TWI690541B - Copolymer - Google Patents

Abstract

The object of the present invention is to provide a novel copolymer having elasticity.

A copolymer which is one or two structural units (a) derived from a hydrophobic monomer having a specific structure and one or two derived from a hydrophilic monomer represented by the following general formula (2) More than one type of structural unit (b) is provided as an essential structural unit, and the weight average molecular weight is 20,000 to 110,000.

Description

Copolymer

The invention relates to a novel copolymer which is a copolymer of a hydrophobic monomer and a hydrophilic monomer.

In addition, the present invention relates to an emulsified composition emulsified by a water-soluble copolymer.

In addition, the present invention relates to a skin cleanser containing a water-soluble copolymer.

In addition, the present invention relates to a sunscreen cosmetic containing a water-soluble copolymer.

In addition, the present invention relates to a film having a sea-island structure in which island particles in which an amphiphilic copolymer is dispersed in the sea of an aqueous gel and a composition forming the same.

Generally speaking, the oil has a good sense of elasticity or moistness, and has been used as a cosmetic material since ancient times. However, on the other hand, the oil agent exerts the above-mentioned excellent use feeling, and when it is highly blended, a sticky feeling may occur and the use feeling may deteriorate.

Under such circumstances, attempts have been made to reduce the stickiness caused by oils by designing the composition or structure of cosmetics. For example, Patent Document 1 proposes a technique for suppressing stickiness in cosmetics emulsified by reducing the emulsified particle size.

However, as described in Patent Document 1, the technique of reducing the stickiness by designing the composition or structure of cosmetics has a problem of being limited to applicable dosage forms.

On the other hand, we propose novel materials that have both a moist feel and a non-sticky feel. For example, Patent Document 2 discloses a base agent for cosmetics containing an alkylene oxide derivative that has both excellent touch and moisturizing properties.

In addition, the emulsified composition in which the oil phase component and the water phase component are mixed with an emulsifier is widely used as a dosage form of cosmetics. However, general low-molecular emulsifiers have problems such as irritation or stickiness to the skin.

In order to solve such problems, various emulsification technologies using polymer emulsifiers have been proposed in recent years.

Patent Document 3 discloses an emulsified composition using hydroxyethyl cellulose as an emulsifier.

In addition, Patent Document 4 discloses an emulsified composition using an alkyl-modified carbopol as an emulsifier.

In addition, in the past, skin cleansers such as facial cleansers have mostly used potassium salts of higher fatty acids from the viewpoint of excellent foaming properties, cleansing power, and refreshing feeling after rinsing. However, skin cleansers that use potassium salts of higher fatty acids as the main component have such excellent properties. On the other hand, they also have difficulty in obtaining dense foam quality. They can easily degrease the skin due to washing, and due to soap scale (scum) ) The problem of remaining on the skin and making the skin easy to tighten after use.

As a method for improving such problems, a combination of higher fatty acids and surfactants such as acetyl taurate type, acetyl isethionate type, phosphate type, and amide amino acid type has been proposed (for example, Patent Literature 5). Blending of additives other than surfactants (for example, silicone compounds or specific glycolipids, raffinose, plant seed slime, various polymer compounds, etc.) (for example, Patent Documents 6 to 12).

In addition, attempts have been made to improve the above-mentioned problems by combining a glycylglycine type surfactant and a specific polymer compound without using the potassium salt of a higher fatty acid as a main component (refer to Patent Document 13).

In addition, the oil-in-water emulsified sunscreen cosmetics have a refreshing feel and are easy to use continuously. In order to improve the UV protection effect, in the oil-in-water emulsified cosmetics, UV absorbers using metal oxide powders such as UV absorbers, zinc oxide or titanium oxide are used. However, when a large amount of ultraviolet absorber is blended, there is a problem that the sense of use such as discoloration, poor elongation, and stickiness is deteriorated. In addition, when a large amount of metal oxide powder is blended, not only does the powder agglomerate and precipitate, etc., with time, but also there is a problem that the viscosity stability, emulsification separation, precipitation, etc. decrease in stability over time. When these are used together, there is a tendency to cause the above-mentioned problems more easily.

In order to improve these problems, it has been proposed to use ultraviolet absorbers such as dibenzoylmethane derivatives and titanium oxide treated with silane and/or silicone (refer to Patent Document 14).

Furthermore, water-in-oil emulsified cosmetics using water-soluble polymers such as polyacrylamide, three gums, (sodium acrylate/acryl dimethyl taurine) copolymer, etc. have been proposed (see Patent Documents 15 and 16).

The island-in-sea structure refers to a structure in which two types of polymers that are incompatible with each other cause phase separation, and a continuous phase (sea phase) containing one polymer is dispersed with a dispersed phase (island phase) containing the other polymer. . As described above, since the sea island structure has a non-uniform structure with phase separation, it has different properties from the composition having a uniform structure. To take advantage of such properties, research and development in the technical field of plastics or rubber, toners, adhesives, etc. are actively carried out for the island structure.

For example, Patent Document 17 discloses a tire that is coated with a coating mixture having a sea-island structure including a marine phase containing a thermoplastic resin and an island phase containing a polyurethane-based thermoplastic elastomer.

However, in the field of cosmetics, attempts to utilize the sea island structure have not been carried out so far.

Then, Patent Document 18 discloses an amphiphilic copolymer containing a structural unit derived from a specific hydrophobic acrylic monomer and a structural unit derived from a specific hydrophilic acrylic monomer External preparation for skin.

Prior technical literature Patent Literature

Patent Literature 1 Japanese Unexamined Patent Publication No. 2012-116783

Patent Document 2 Japanese Reissue Table 2006/038724

Patent Literature 3 Japanese Patent Laid-Open No. 2011-231049

Patent Document 4 Japanese Patent Laid-Open No. 09-019631

Patent Literature 5 Japanese Patent Laid-Open No. 6-248298

Patent Document 6 Japanese Patent Laid-Open No. 10-77206

Patent Document 7 Japanese Patent Laid-Open No. 2001-72574

Patent Document 8 Japanese Patent Laid-Open No. 2000-178172

Patent Document 9 Japanese Patent Laid-Open No. 11-209799

Patent Literature 10 Japanese Patent Application Publication No. 2003-73257

Patent Literature 11 Japanese Patent Application Publication No. 2007-277140

Patent Document 12 Japanese Patent Laid-Open No. 10-183193

Patent Document 13 Japanese Patent Laid-Open No. 9-78082

Patent Document 14 Japanese Patent Laid-Open No. 9-2929

Patent Literature 15 Japanese Patent Application Publication No. 2003-104859

Patent Document 16 Japanese Patent Application Publication No. 2010-215602

Patent Literature 17 Japanese Patent Application Publication No. 2013-180652

Patent Literature 18 Japanese Patent Application Publication No. 2014-9189

As mentioned above, the oil has a better sense of elasticity on the other hand, it also has problems such as stickiness. Under such circumstances, new materials with elasticity like oils are needed.

The object of the present invention is to provide a novel copolymer having elasticity. Furthermore, in a preferred embodiment of the present invention, it is the first problem to provide a copolymer which does not easily produce a sticky feeling and has a moist feeling.

Furthermore, the above-mentioned polymer emulsifier has less irritation to the skin and has the advantages of less stickiness when contained in a low concentration, but when compared with the conventional low-molecular emulsifier, the emulsifying power is poor. Therefore, in order to ensure the stability of the emulsified state, a high-molecular emulsifier blended with an emulsified composition is required, which becomes a high viscosity, and as a result, has a problem of stickiness.

In view of such circumstances, the present invention will provide an emulsified composition with less irritation to the skin, less stickiness, and good emulsification stability as the second subject.

Due to the surge in consumer demand in recent years, especially with regard to foam quality or touch after cleaning, these methods have not been fully satisfied and further improvements are needed.

In view of such circumstances, the third problem to be solved by the present invention is to provide a novel technology that can reduce the tightness of the skin after the use of the skin cleanser.

In addition, it will provide a beneficial effect of the original skin cleanser that does not impair cleansing power, good foaming quality, good foam quality, non-sticky and slippery feeling after use, and ease of extension to the skin, etc., and The technology that can reduce the tightness of the skin after use is the fourth issue.

Furthermore, in the technical field of oil-in-water sunscreen cosmetics, it is a problem to have both ultraviolet protection function and sense of use or emulsion stability. In the past, various technologies have been proposed to solve this problem, but this is not enough.

In view of such circumstances, the fifth problem to be solved by the present invention is to provide an oil-in-water sunscreen cosmetic that has good ultraviolet protection function, has no sticky feeling or moisturizing feeling, and has good emulsification stability. .

In addition, the problem to be solved by the present invention is to provide a film having a sea-island structure mainly composed of a water-soluble component and a technique for forming the film. In addition, we will provide a lesson in the film that uses water-soluble ingredients as the main body to give a touch to milk such as oil. question. Preferably, it is the sixth subject of the present invention to provide a coating having both moisture retention and flexibility and a technique for forming the coating.

In view of the state of being the background of the first subject, the inventors of the present application have pursued a stretch-sensitive copolymer and conducted careful research. As a result, they have found that: a hydrophobic, polymerizable carboxyl group and two acrylate groups with a specific branched structure are mono- The copolymer of the polymer and the hydrophilic acrylic monomer having a specific structure has good solubility, especially good solubility in water, and has an elastic feel like an oil agent, thereby completing the present invention. That is, the present invention is as follows.

A copolymer comprising one or two or more structural units (a) derived from a hydrophobic monomer represented by the following general formula (1) and a hydrophilic monomer represented by the following general formula (2) One or two or more types of structural units (b) derived from the body are required as structural units, and the weight average molecular weight is 20,000 to 110,000.

(In general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² and R ³ may be the same or different, and represents a branched carbon number having 6 to 22 that does not contain a ring structure. Acyl group. X represents a group desorbing an OH group from a triol).

(In the general formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁶ represents a hydrogen atom and a carbon atom having 6 to 6 carbon atoms. 10 aromatic hydrocarbon groups, aliphatic hydrocarbon groups having 1 to 14 carbon atoms or acyl groups having 1 to 12 carbon atoms. n represents an integer of 6 to 40).

Such a copolymer has an elastic feeling when applied to the skin, and has a non-sticky or moist feeling.

In a preferred embodiment of the present invention, the mass ratio of the structural unit (a) to the structural unit (b) is 25:75 to 35:65.

The copolymer having a mass ratio of the structural unit (a) to the structural unit (b) within the aforementioned range has good elasticity and non-sticky feel.

In a preferred embodiment of the present invention, the molar ratio of the structural unit (a) to the structural unit (b) is 35:65 to 46:54.

The molar ratio of the structural unit (a) and the structural unit (b) is a copolymer in the aforementioned range, and the elasticity feeling and the stickiness-free feeling are excellent.

In a preferred embodiment of the present invention, the hydrophobic monomer is a hydrophobic monomer represented by the following general formula (3).

Formula (3)

(In general formula (3), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁸ and R ⁹ may be the same or different, and represents a branched carbon number having 10 to 22 carbon atoms that does not contain a ring structure. An acyl group, or an acyl group having 6 or more carbon atoms that does not contain a ring structure and has 2 or more branches. Y represents a group that desorbs an OH group from a triol).

As the hydrophobic monomer, by using the aforementioned monomer, it can become a copolymer having more excellent touch.

Furthermore, in a preferred embodiment of the present invention, the hydrophilic monomer is a hydrophilic monomer represented by the following general formula (4).

(In general formula (4), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ¹¹ represents a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 14 carbon atoms or carbon The number is 1~12 of acetyl group. m represents an integer of 6~40).

As the hydrophilic monomer, by using the aforementioned monomer, it can become a copolymer having a more excellent touch.

In a preferred embodiment of the present invention, the triol is glycerin, trimethylolpropane, and trimethylolethane.

By becoming such a form, the sense of elasticity can be improved.

The aforementioned hydrophobic monomer is a compound represented by the following general formula (5).

(In the general formula (5), R ¹² and R ¹³ may be the same or different, and represent a branched C 18 acyl group that does not contain a ring structure).

By using such a hydrophobic monomer, the elasticity can be improved.

In a preferred embodiment of the present invention, the hydrophilic monomer is a hydrophilic monomer represented by the following general formula (6).

(In the general formula (6), l represents an integer of 6 to 40).

By using such a hydrophilic monomer, the elasticity can be improved.

In addition, the present invention also relates to an external preparation for skin containing the copolymer of the present invention. This external preparation for skin has an elastic feeling after being applied to the skin. Also, there is no sticky or moist feeling.

The present invention for solving the second problem is an emulsified composition containing one or more types derived from a hydrophobic monomer represented by the aforementioned general formula (1), (7) or (8) below The structural unit (c) and one or more structural units (d) derived from a hydrophilic monomer are water-soluble copolymers that are essential structural units and do not substantially contain emulsifiers other than the water-soluble copolymer .

(In the general formula (7), R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁵ represents a branched hydrocarbon group having 13 to 30 carbon atoms which does not contain a ring structure, or 2 which does not contain a ring structure. (The above branches have 6 to 12 hydrocarbon groups).

Formula (8)

(In the general formula (8), R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁷ , R ¹⁸ , and R ¹⁹ may be the same or different, and represents a branched carbon number 6 that does not contain a ring structure. ~22 acyl group. Y represents a group desorbing OH group from a tetrahydric alcohol).

The emulsified composition of the present invention contains the above-mentioned water-soluble copolymer, and has less stickiness during use.

In a preferred embodiment of the present invention, the hydrophilic monomer is selected from the group consisting of a polymerizable carboxylic acid, a hydrophilic monomer represented by the above general formula (2), and a hydrophilic property represented by the following general formula (9) One type, or two or more types of hydrophilic monomers of a monomer, a hydrophilic monomer represented by the following general formula (10), and a hydrophilic monomer represented by the following general formula (11).

(In the general formula (9), R ²⁰ represents a hydrogen atom or a methyl group).

Formula (10)

(In the general formula (10), R ²¹ represents a hydrogen atom or a methyl group, GO- represents a group in which hydrogen is removed from the hydroxyl group at the 1-position of the reducing sugar. m represents an integer of 2 or 3, and l represents an integer of 1 to 5).

(In the general formula (11), R ²² represents a hydrogen atom or a methyl group, and R ²³ represents an amino acid residue, a polyamine residue, or an amino alcohol residue. Q represents an oxygen atom or a group represented by NH).

By including the water-soluble copolymer containing the structural unit (d) derived from such a hydrophilic monomer, the sticky feeling during use of the emulsified composition of the present invention can be further reduced.

In a preferred embodiment of the present invention, the hydrophobic monomer is a hydrophobic monomer represented by the general formula (1), and the water-soluble monomer is a hydrophilic monomer represented by the general formula (2).

The water-soluble copolymer containing structural units derived from such a hydrophobic monomer and a hydrophilic monomer has a good emulsifying power, and has a good effect of reducing the sticky feeling when using the emulsified composition of the present invention.

In a preferred embodiment of the present invention, the content of the water-soluble copolymer is 0.5 to 30% by mass.

By setting the content of the water-soluble copolymer to the aforementioned range, the stability of the emulsified composition can be improved.

In a preferred form of the present invention, the content of the oil phase component is 0.1 to 70% by mass.

The emulsified composition of the present invention in which the content of the oil phase component is in the aforementioned range is excellent in stability.

The emulsified composition of the present invention has less stickiness and is therefore suitable as a cosmetic.

In addition, the present invention also relates to a structural unit (c) including one or more structural units derived from the hydrophobic monomer represented by the general formula (1), (7) or (8) and a self-hydrophilic monomer One type or two or more types of structural units (d) derived from the polymer are used as an emulsifier of the water-soluble copolymer that the necessary structural units have.

The emulsifier is low in irritation and at the same time has excellent emulsifying power.

In addition, the present invention also relates to a manufacturing method, which is a manufacturing method of an emulsified composition including the step of emulsification using the emulsifier, and is characterized in that substantially no emulsifier other than the emulsifier is used.

According to this method, a conventional emulsifier that gives a sticky feeling is not used, and an emulsified composition can be easily produced even if the emulsifier is not highly blended.

The present invention for solving the third and fourth problems is to include one or more structural units (e) derived from the hydrophobic monomer represented by the general formula (1), (7) or (8) and One or two or more structural units (f) derived from a hydrophilic monomer are used as a skin cleansing agent of a water-soluble copolymer having essential structural units.

The skin cleansing agent of the present invention, by containing the water-soluble copolymer, has good foaming properties and dense foam quality, and at the same time can reduce the tightness after use.

In a preferred embodiment of the present invention, the hydrophilic monomer is selected from the group consisting of a polymerizable carboxylic acid, a hydrophilic monomer represented by the general formula (2), and a hydrophilic monomer represented by the general formula (9). 1 type, or 2 or more types of hydrophilic monomers of the group, the hydrophilic monomer represented by the general formula (10), and the hydrophilic monomer represented by the general formula (11).

By including the water-soluble copolymer containing the structural unit (e) derived from such a hydrophilic monomer, the tightness of the skin cleansing agent of the present invention after use can be further reduced.

In a preferred embodiment of the present invention, the hydrophobic monomer is a hydrophobic monomer represented by the general formula (1), and the water-soluble monomer is a hydrophilic monomer represented by the general formula (2).

By including a water-soluble copolymer having structural units derived from such a hydrophobic monomer and a hydrophilic monomer, the tightness of the skin cleansing agent of the present invention after use can be further reduced.

In an embodiment of the present invention, the content of the water-soluble copolymer is 0.1 to 20% by mass.

By setting the content of the water-soluble copolymer to the aforementioned range, the stickiness of the skin cleanser of the present invention when used can be reduced.

The invention is preferably applied to foaming detergents.

According to the present invention, it does not hinder the foamability or foam quality of the foaming cleanser, and can reduce the tightness of the skin after use.

The invention is preferably applied to gel-like skin cleansers.

According to the present invention, the ease of extension of the gel-like skin cleanser on the skin can be improved, and at the same time, the tightness of the skin after use can be reduced.

Because skin cleansers containing surfactants have a higher cleaning power, the tightness after use is also stronger. Therefore, the present invention is preferably applied to skin cleansers containing surfactants. According to the present invention, the excellent cleansing power of the surfactant is not compromised, or the cleansing power of the skin cleanser after use can be reduced while improving the cleansing power.

Skin cleansers containing fatty acid soaps have good foaming properties, dense foam quality, and good cleansing power, but they feel a strong sense of tightness after use. Therefore, the present invention is preferably applied to a skin cleanser containing fatty acid soap. According to the present invention, the beneficial effects of skin cleansers containing fatty acid soaps are not compromised, and the tightness of the skin after use can be reduced.

In a preferred embodiment of the present invention, the content ratio of the water-soluble copolymer to the fatty acid soap is 1:500~1:2, preferably 1:200~1:3, more preferably 1:100~ 1:5.

By setting the content of the water-soluble copolymer to the aforementioned range, it is possible to more effectively reduce the tightness of the skin cleanser containing fatty acid soap after use.

The present invention is also preferably applied to skin cleansers containing nonionic surfactants.

According to the present invention, the cleansing power of a skin cleanser containing a nonionic surfactant is improved, and at the same time, the tightness of the skin after use can be reduced.

In a preferred embodiment of the present invention, the content ratio of the water-soluble copolymer to the nonionic surfactant is 1:20~1:0.5, preferably 1:15~1:0.7, more preferably 1:10~1:1.

By setting the content ratio of the water-soluble copolymer to the nonionic surfactant to the aforementioned range, the tightness after use can be more effectively reduced.

The present invention that solves the fifth problem is an oil-in-water sunscreen cosmetic containing components (A) to (D).

(A) One or more structural units (g) derived from the hydrophobic monomer represented by the general formula (1), (7) or (8) and one derived from the hydrophilic monomer Or a water-soluble copolymer having two or more kinds of structural units (h) as essential structural units

(B) Polyglycerol fatty acid ester formed by condensation of 1 molecule of polyglycerol with a polymerization degree of 10 and 2 to 5 molecules of fatty acid with carbon number of 16 or more

(C) Ionic surfactant

(D) UV scattering agent and/or UV absorber

The sunscreen cosmetics of the present invention have ultraviolet protection function, meanwhile, they have less sticky feeling and good moisturizing properties. In addition, the sunscreen cosmetic of the present invention has emulsification stability.

In a preferred embodiment of the present invention, the hydrophilic monomer is selected from the group consisting of a polymerizable carboxylic acid, a hydrophilic monomer represented by the general formula (2), and a hydrophilic monomer represented by the general formula (9). Body, represented by the above general formula (10) One or more hydrophilic monomers of the group of the hydrophilic monomer and the hydrophilic monomer represented by the general formula (11).

By using the water-soluble copolymer containing the structural unit (h) derived from such a hydrophilic monomer, the sense of use such as less sticky feeling or moisturizing feeling can be improved.

In a preferred embodiment of the present invention, the hydrophobic monomer is a hydrophobic monomer represented by the general formula (1), and the water-soluble monomer is a hydrophilic monomer represented by the general formula (2).

Sunscreen cosmetics containing water-soluble copolymers having structural units derived from such hydrophobic monomers and hydrophilic monomers have a more excellent sense of use.

In a preferred embodiment of the present invention, the aforementioned component (C) is an anionic surfactant.

As an ionic surfactant, by using an anionic surfactant, emulsification stability can be further improved. In addition, the sunscreen cosmetics of the present invention using an anionic surfactant also have a good feeling of use.

In a preferred embodiment of the present invention, the anionic surfactant is sodium acyl lactylate.

As an anionic surfactant, by using sodium acylate lactate, the stability of emulsification can be further improved. In addition, the sunscreen cosmetics of the present invention using sodium acyl lactylate have a good feeling of use.

In a preferred embodiment of the present invention, the aforementioned component (B) is polyglyceryl pentastearate-10.

The sunscreen cosmetic of the present invention containing polyglycerol pentastearate-10 has excellent emulsification stability and feeling of use.

In a preferred embodiment of the present invention, the aforementioned component (D) is a water-dispersible ultraviolet scattering agent.

Because the water-dispersible ultraviolet scattering agent is uniformly dispersed in the water phase, the sunscreen cosmetic of the present invention in such a form has a good ultraviolet defense function.

In a preferred embodiment of the present invention, the water-dispersible ultraviolet scattering agent is an ultraviolet scattering agent surface-treated with sodium polyacrylate.

As in the sunscreen cosmetics of the aforementioned form, the ultraviolet scattering agent is more evenly dispersed, and the ultraviolet protection function is good.

The present invention that solves the sixth problem is to include one or more structural units (i) derived from a hydrophobic monomer and one or more structural units (j) derived from a hydrophilic monomer as The amphiphilic copolymer, water-soluble polymer and/or salt thereof, and water necessary in the constituent unit are evaporated in the water to form an aqueous gel formed by the water-soluble polymer and/or salt thereof. A composition having a film having a sea-island structure in which island particles containing the amphiphilic copolymer are dispersed is formed.

The aforementioned film has a sea-island structure mainly composed of water-soluble components, and has a tactile feel like milk containing oil. According to the composition of the present invention, a film having such a sea-island structure can be formed on the skin.

In a preferred embodiment of the present invention, the island particles have an average long axis to short axis ratio of 0.8 or more, and the particle size distribution of the island particles having an average particle size of 1 to 5 μm is 80% or more.

The aforementioned coating film having such structural characteristics has excellent moisture retention and flexibility.

Then, by applying the composition of the present invention to the skin, a film having such excellent properties can be easily formed.

In a preferred embodiment of the present invention, the water-soluble polymer is one or more water-soluble polymers selected from the group consisting of acrylic water-soluble polymer, water-soluble polypeptide and water-soluble polysaccharide. And/or its salts.

By adopting such a form containing a water-soluble polymer, the water solubility of the components of the composition can be improved, and by suppressing the occurrence of precipitation, the stability of the composition can be improved.

In a preferred embodiment of the present invention, the water-soluble polymer is selected from the group consisting of sodium polyacrylate, (acrylate/alkyl acrylate (C10-30)) cross-linked polymer, sodium polyglutamine, and sanxian gum One or more water-soluble polymers in the group of Tremella polysaccharides.

By adopting such a form containing a water-soluble polymer, the stability of the composition can be further improved.

In a preferred embodiment of the present invention, the composition includes a polyol that promotes phase separation of the aqueous gel and the amphiphilic copolymer and/or an inhibitor that inhibits the aqueous gel and the amphiphilic copolymer Phase separated polyol.

By including such a polyol, the uniformity of the aforementioned coating can be improved.

In a preferred embodiment of the present invention, the aforementioned phase separation-promoting polyol is mixed with an aqueous solution of a nonionic surfactant having a polyether chain in the hydrophilic part, so that the cloud point of the aqueous solution is much increased. Monohydric alcohol; the aforementioned polyol that inhibits phase separation is a polyol that reduces the cloud point of the aqueous solution by mixing with an aqueous solution of a nonionic surfactant having a polyether chain in the hydrophilic portion.

By including such a polyol, the uniformity of the aforementioned coating can be improved.

In a preferred embodiment of the present invention, the polyol for promoting phase separation is one or more polyols selected from the group consisting of 1,3-butanediol and polyethylene glycol.

By using such a polyol, the phase separation of the aqueous gel and the amphiphilic copolymer can be effectively promoted, and the uniformity of the aforementioned coating can be improved.

In a preferred embodiment of the present invention, the polyhydric alcohol that inhibits phase separation is one or more polyhydric alcohols selected from the group consisting of glycerin, diglycerin, sorbitol, and maltitol.

By using such a polyol, the phase separation of the aqueous gel and the amphiphilic copolymer can be effectively promoted, and the uniformity of the aforementioned coating can be improved.

In a preferred embodiment of the present invention, the mass ratio of the total amount of the phase separation promoting polyol and the phase separation suppression polyol to the total amount of the amphiphilic copolymer and the water soluble polymer is 5: 1~20:1.

By adopting such a shape, the uniformity of the aforementioned coating can be improved.

In a preferred embodiment of the present invention, the mass ratio of the phase separation promoting polyol and the phase separation inhibiting polyol is 3.5:1 to 1:2.5.

By adopting such a shape, the uniformity of the aforementioned coating can be improved.

In a preferred embodiment of the present invention, the content of the amphiphilic copolymer is 0.1 to 5% by mass.

By making the content of the amphiphilic copolymer into the aforementioned range, it can be further formed into a composition capable of forming the aforementioned coating film having excellent soft touch.

In a preferred embodiment of the present invention, the content of the oil agent is 1% by mass or less.

By adopting such a form, it becomes a composition capable of forming the aforementioned coating film with little stickiness.

In a preferred embodiment of the present invention, the amphiphilic copolymer includes one or more copolymers selected from Group E below.

Group E: polyquaternium-51, polyquaternium-61, (glyceryl methacrylate ethyl ester/stearyl methacrylate) copolymer, and selected from general formula (1), ( 7) Acrylic amphiphilic copolymer of structural unit (i) derived from hydrophobic monomer of (8)

The composition of the present invention containing such an amphiphilic copolymer, such as milk, has a stronger touch and can form the aforementioned coating film having better flexibility.

In a preferred embodiment of the present invention, the acrylic amphiphilic copolymer includes a structural unit (j) derived from one or more hydrophilic monomers selected from Group F below.

Group F: polymerizable carboxylic acid, copolymer represented by the general formula (2), copolymer represented by the general formula (9), copolymer represented by the general formula (10), and the general formula (11) Copolymer shown

The composition of the present invention containing an amphiphilic copolymer having a structural unit (j) derived from such a hydrophilic monomer has a stronger tactile feel, and can form the aforementioned coating film having better flexibility.

In a preferred embodiment of the present invention, the acrylic amphiphilic copolymer includes a structural unit (i) derived from the hydrophobic monomer represented by the general formula (1) and a component derived from the general formula (2) The structural unit (j) derived from the hydrophilic monomer shown.

According to the composition of the present invention containing such an acrylic amphiphilic copolymer, the aforementioned coating film having excellent moisture retention and flexibility can be further formed.

In addition, the present invention also relates to a film having a sea-island structure in which island particles containing an amphiphilic copolymer are dispersed in an aqueous gel formed of a water-soluble polymer. The amphiphilic copolymer will be One or more structural units (i) derived from a hydrophobic monomer and one or more structural units (j) derived from a hydrophilic monomer are contained as necessary structural units.

The coating of the present invention has a sea-island structure mainly composed of water-soluble components. Then, regardless of whether the water-soluble component is the main component, it has a touch like milk containing oil.

In a preferred embodiment of the present invention, the island particles have an average long axis to short axis ratio of 0.8 or more, and the particle size distribution of the island particles having an average particle size of 1 to 5 μm is 80% or more.

The aforementioned coating film having such structural characteristics, such as milk containing oil, has a good touch.

In addition, the present invention also relates to a method of forming the above-mentioned coating film of the present invention, comprising one or more structural units derived from a hydrophobic monomer (i) and 1 derived from a hydrophilic monomer One or two or more types of structural units (j) are applied to the skin as a composition of the amphiphilic copolymer, water-soluble polymer and/or its salt, and water as essential structural units.

According to the method of the present invention, the aforementioned coating can be easily formed.

Furthermore, in a preferred embodiment of the present invention, the composition includes a polyol that promotes phase separation of the amphiphilic copolymer and the aqueous gel and/or inhibits the copolymerization of the aqueous gel and the amphiphilic copolymer The phase separated polyol.

By using an aqueous solution containing such a polyhydric alcohol, the aforementioned coating film with good uniformity can be formed.

According to the present invention, a copolymer having elasticity and an external preparation for skin can be provided.

In addition, according to the present invention, it is possible to provide an emulsified composition which has less irritation to the skin, less stickiness, and excellent emulsification stability.

Furthermore, according to the present invention, it is possible to provide a skin cleanser with reduced tightness after use.

In addition, when the present invention is applied to a skin cleanser containing fatty acid soaps, it does not hinder good foaming properties or dense foam quality, and can reduce tightness after use.

In addition, when the present invention is applied to a gel-like skin cleanser, an effect of reducing tightness after use can also be obtained.

In addition, according to the present invention, it is possible to provide an oil-in-water sunscreen cosmetic which has a good ultraviolet protection function, has no sticky feeling or moisturizing feeling, and has emulsification stability.

Furthermore, according to the present invention, it is possible to provide a film having a sea-island structure mainly composed of a water-soluble component and a technique for forming the film. The aforementioned coating, regardless of whether or not the water-soluble component is the main component, has a touch like milk containing oil.

In addition, in a preferred embodiment of the present invention, the aforementioned coating film without stickiness and a technique for forming the coating film can be provided.

1‧‧‧Example 103

2‧‧‧Example 104

3‧‧‧Example 105

4‧‧‧Example 106

5‧‧‧Example 107

6‧‧‧Example 108

7‧‧‧Example 109

8‧‧‧Example 110

9‧‧‧Example 111

10‧‧‧Example 112

11‧‧‧Example 113

12‧‧‧Example 114

13‧‧‧Example 115

14‧‧‧Example 116

15‧‧‧Example 117

16‧‧‧Example 118

17‧‧‧Example 119

18‧‧‧Example 120

19‧‧‧Example 121

20‧‧‧Example 122

21‧‧‧Example 123

FIG. 1 is a bar graph showing the evaluation results of gel-like cosmetics including the copolymers of Example 1 and Comparative Example 1. FIG.

Figure 2 shows the blending ratio of the glycerin diisostearate methacrylate/methacrylic acid PEG-23 copolymer of Examples 9 to 31, squalane and water. Composition diagram.

Figure 3 shows the copolymers of Examples 32-62 (glyceryl diisostearate methacrylate/methacrylic acid PEG-23) and tris(octanoic acid/capric acid) glyceride and water The three components of the blend ratio mapping are phase diagrams.

Fig. 4 shows the blending ratio of the copolymers of (glyceryl diisostearate methacrylate/methoxymethyl propionate PEG-23) of Examples 63 to 89, dimethicone and water The 3-component phase diagram of cartography.

Figure 5 shows the 1,3-butanediol, glycerin, tannin gum and (methacrylic acid methyl ester PEG-23/diisostearate glycerol methacrylate contained in Examples 104-124) The three-component phase diagram of the total amount of ester) copolymer.

Fig. 6 shows micrographs of the compositions of Examples 105, 106, 108, 111, 113, 114, 115, 119, 120, 122, and 123.

FIG. 7 shows a pie chart showing the results of tactile evaluation of the composition of Example 104 of Test Example 7. FIG.

[Forms for carrying out the invention]

The copolymer of the present invention for solving the first problem is composed of one or two or more structural units (a) derived from the hydrophobic monomer represented by the aforementioned general formula (1) and the following general formula (2) One or two or more structural units (b) derived from the hydrophilic monomers shown are included as essential structural units.

Furthermore, in the present invention, "constituent unit derived from a monomer" refers to a constituent unit formed by cleaving a carbon-carbon unsaturated bond possessed by the corresponding monomer by a polymerization reaction.

Hereinafter, the hydrophobic monomer represented by the general formula (1) and the hydrophilic monomer represented by the general formula (2) will be described.

<1> Hydrophobic monomer

The copolymer of the present invention contains one or two or more structural units derived from the hydrophobic monomer represented by the general formula (1) (hereinafter sometimes simply referred to as "constituent unit (1)") as essential structural units.

Here, examples of the alkyl group represented by R ¹ include methyl, ethyl, propyl, isopropyl, and cyclopropyl. In the present invention, R ¹ is preferably hydrogen or methyl.

In addition, examples of R ² and R ^{3 that} do not contain a ring structure and have branched C 6-22 acyl groups include 2-methylpentyl group, 3-methylpentyl group, and 4-methyl group. Pentamyl, 2-ethylbutyryl, 2,2-dimethylbutyryl, 3,3-dimethylbutyryl, 2-methylhexyl, 4-methylhexyl, 5-methylhexyl Group, 2,2-dimethylpentyl group, 4,4-dimethylpentyl group, 2-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, 2,2- Dimethylhexyl, 2,2,3-trimethylpentyl, 2-methyloctyl, 3,3,5-trimethylhexyl, 2-methylnonyl, 4-methyl Ylnonyl, 8-methylnonyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2-third butylhexyl, 2,2-diethyl Hexamyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methyldecyl, 2-methyl-2-ethyloctyl, 2-methyl Undecylenyl, 10-methylundecyl, 2,2-dimethyldecyl, 2-ethyldecyl, 2-butyloctyl, diethyloctyl, 2-third butyl -2,2,4-trimethylpentanyl, 10-methyldodecyl, 3-methyldodecyl, 4-methyldodecyl, 11-methyldodecyl, 10-ethylundecyl, 12-methyltridecyl, 2-butyldecyl, 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-methyltetradecyl , 14-methylpentadecyl, 2-butyldodecyl, 2-hexyldecyl, 16-methylheptadecyl, 2,2-dimethylhexyl, 2-butyl Hexadecyl, 2-hexyldodecyl, 2,4,10,14-tetramethylpentyl, 18-methyl nonadecyl, 3,7,11,15-tetra-methyl deca Hexaacetyl, 19-methyl eicosyl, etc.

In a more preferred embodiment of the present invention, the hydrophobic monomer represented by the general formula (1) is the hydrophobic monomer represented by the general formula (3).

As such a preferred embodiment, R ⁸ and R ^{9 which} do not contain a ring structure and have a branched carbon number of 10 to 22 acyl group, can be exemplified by 2-methylnonyl group, 4-methylnonyl group , 8-methylnonanoyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2-third butylhexyl, 2,2-diethylhexyl, 2,2-Dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methyldecyl, 2-methyl-2-ethyloctyl, 2-methylundecyl , 10-methylundecyl, 2,2-dimethyldecyl, 2-ethyldecyl, 2-butyloctyl, diethyloctyl, 2-third-butyl-2,2 ,4-trimethylpentyl acetyl, 10-methyl dodecyl, 3-methyl dodecyl, 4-methyl dodecyl, 11-methyl dodecyl, 10-ethyl Undecylenyl, 12-methyltridecyl, 2-butyldecyl, 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-methyltetradecyl, 14-methyl Ethyl pentadecyl, 2-butyldodecyl, 2-hexyldecyl, 16-methylheptadecyl, 2,2-dimethylhexyl, 2-butylhexadecyl , 2-hexyldodecyl, 2,4,10,14-tetramethylpentyl, 18-methyl nonadecyl, 3,7,11,15-tetra-methylhexadecyl, 19-methyl eicosyl, etc.

In addition, as a preferred embodiment, R ⁸ and R ^{9 which} do not contain a ring structure and have 2 or more branches of C 6-9 acryloyl groups can be exemplified by 2,2-dimethylbutyroyl, 3 ,3-dimethylbutyryl, 2,2-dimethylpentyl, 4,4-dimethylpentyl, 2,2-dimethylhexyl, 2,2,3-trimethyl Pentyl, 3,5,5-trimethylhexyl, etc.

The carbon number of the acyl group of R ⁸ and R ^{9 in} the general formula (3) is preferably 12-22, more preferably 14-20, and particularly preferably 16-20.

In addition, the carbon number of the main chain of the acyl group of R ⁸ and R ^{9 in} the general formula (3) is preferably 9 to 21, more preferably 12 to 20, and particularly preferably 16 to 18.

In addition, the number of branching of the acyl group of R ⁸ and R ^{9 in} the general formula (3) is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

In addition, in the acyl group of R ⁸ and R ⁹ in the general formula (3), the larger the position number of the carbon of the main chain of the branch chain bonding, the better. Specifically, the branched chain is preferably bonded to the first to third carbons at the end of the autonomous chain, more preferably the first or second carbon, and particularly preferably the first carbon.

As R ⁸ and R ⁹ , specifically, 10-methyl undecyl group, 10-methyl dodecyl group, 11-methyl dodecyl group, 10-ethyl undecyl group, 12-Methyltridecyl, 12-methyltetradecyl, 14-methylpentadecyl, 16-methylheptadecyl, 2,4,10,14-tetramethylpentyl , 18-methyl nineteen amide, 3,7,11,15-tetra-methyl hexadecyl, 19-methyl eicosyl, etc.

In the aforementioned general formulas (1) and (3), the group derived from triol represented by X or Y is not particularly limited as long as it is a group from which the OH group is desorbed from the triol, and can be appropriately exemplified from The OH group is desorbed from the triol including glycerin, trimethylolpropane, and trimethylolethane.

In a preferred embodiment of the present invention, it is preferable to use the monomer represented by the general formula (5) as the hydrophobic monomer.

As the hydrophobic monomer represented by the general formula (5), compounds represented by the following formulas (12) to (14) can be exemplified. It is preferable to use a compound represented by the following formula (12) in which a branched chain is added to the terminal of the acyl group.

式(13)

Formula (13)

The hydrophobic monomer represented by the general formula (1) constituting the copolymer of the present invention can be synthesized, for example, by the following method.

a) Ketalize the triol. As a specific synthesis method, for example, the method described in Production Example 1 of Japanese Patent Laid-Open No. 2009-136749 can be exemplified.

b) Transesterification of the ketalized triol synthesized in a with alkyl (meth)acrylate to synthesize the (meth)acrylate of the ketal and remove the (meth)acrylate of the obtained ketal Ketone reaction to synthesize mono(meth)acrylate of triol. As a specific synthesis method, for example, the method described in Example 1 of Japanese Patent Laid-Open No. 2004-18389 can be exemplified.

c) The mono(meth)acrylate of the triol obtained in b is reacted with a carboxylic acid having a predetermined branch structure or its anhydride or its chloride to obtain a hydrophobic monomer represented by the general formula (1).

In addition, since a commercial product is also present in the ketalized triol, the commercial product can also be used, and the ester of the triol of the present invention can be obtained by the above steps b) and c). As such a commercially available product, (S)-(+)-2,2-dimethyl-1,3-dioxolane-4-methanol, (R)-(+)-2,2 can be exemplified -Dimethyl-1,3-dioxolane-4-methanol (both Tokyo Chemical industry (stock) system). In addition, since a commercially available product also exists in the mono(meth)acrylate of the triol, the commercially available product can also be used, and the ester of the triol of the present invention can be obtained by the above step c). As such a commercially available product, "Blenmer GLM" (made by glycerin monomethacrylate Nippon Oil & Fats Co., Ltd.) can be exemplified.

The proportion of the structural unit (a) of the copolymer of the present invention in all the structural units is preferably 1 to 40% by mass, more preferably 5 to 35% by mass.

By making the ratio of the structural unit (a) within the aforementioned range, the elasticity of the copolymer of the present invention can be improved.

<2> Hydrophilic monomer

The copolymer of the present invention contains one or more structural units derived from the hydrophilic monomer represented by the aforementioned general formula (2) as essential structural units.

Examples of the alkyl group represented by R ⁴ in the general formula (2) include methyl, ethyl, propyl, isopropyl, and cyclopropyl. In the present invention, R ⁴ is preferably a hydrogen atom or a methyl group.

In addition, examples of the alkylene group represented by R ⁵ include ethyl group, ethyl group, isopropyl group, 2-hydroxypropyl group, 1-hydroxy-2-methyl ethyl group, and 2-hydroxy- 1-methylethylidene, etc., but among these, ethylidene or propylidene are preferred, and ethylidene is more preferred.

In addition, among the groups represented by R ⁶ , examples of the aromatic groups having 6 to 10 carbon atoms include phenyl, benzyl, tolyl, and ethylphenyl groups. As the aliphatic hydrocarbon groups having 1 to 14 carbon atoms, Appropriate examples include methyl, ethyl, butyl, tertiary butyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, lauryl, etc.; as a C 1-12 acyl group, a methyl acyl group can be appropriately exemplified. , Acetyl, propyl, butyl, isobutyl, pentyl, lauryl, etc. Among these, the group represented by R ^{5 is} preferably an aliphatic hydrocarbon group having 1 to 14 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.

Furthermore, n in the general formula (2) is in the range of 6 to 40.

Among the monomers represented by the general formula (2), as the monomer in which R ⁵ is propylene, specifically, polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, poly Propylene glycol (9) monomethacrylate, polypropylene glycol (13) monomethacrylate, etc. Furthermore, the number in parentheses indicates N. Most of these polymers are available as commercial products. Specific examples of these commercially available products include trade names "Blenmer" AP-400, AP-550, AP-800, PP-500, and PP-800 (all manufactured by Nippon Oil & Fats Co., Ltd.).

Among the monomers represented by the general formula (2), as the monomer in which R ⁵ is an ethylidene group, specifically, polyethylene glycol (10) monoacrylate, polyethylene glycol (8) monomer Methacrylate, polyethylene glycol (23) monoacrylate, polyethylene glycol (23) monomethacrylate, methoxypolyethylene glycol (9) acrylate, methoxypolyethylene glycol ( 9) Methacrylate, methoxypolyethylene glycol (23) methacrylate, oleyloxy polyethylene glycol (18) methacrylate, lauryloxy polyethylene glycol (18) acrylate, Lauryloxy polyethylene glycol (10) methacrylate, stearyl polyethylene glycol (30) monomethacrylate, etc.

In a preferred embodiment of the present invention, as the hydrophilic monomer, the monomer represented by the general formula (6) is used.

1 in the aforementioned general formula (6) is preferably 6-30, and more preferably 8-30.

The above-mentioned hydrophilic monomers can be obtained in a high yield by esterification reaction of corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride. In addition, since many commercial products already exist, the commercial products can also be used. As such a commercially available product, specifically, the trade names of Blenmer, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, and PSE-1300 (all of which are Japanese oil ) System) etc.

The structural unit derived from the hydrophilic monomer contained in the copolymer of the present invention may be only one type, but as long as the aforementioned conditions are satisfied, two or more types of structural units may be combined and contained.

The proportion of the structural unit (b) derived from the hydrophilic monomer of the copolymer of the present invention in all the structural units is 30 to 95% by mass, preferably 40 to 90% by mass.

By making the ratio of the structural unit (b) within the aforementioned range, the elasticity of the copolymer of the present invention can be improved.

<3> Any other constituent unit

The copolymer of the present invention may contain, as well as the above-mentioned structural unit 1 and structural unit 2, units derived from monomers which are generally used in copolymers, as arbitrary structural units within a range that does not impair the effects of the invention. Examples of the arbitrary constituent unit include amide (meth)acrylate and methyl (meth)acrylate from amide acrylate, amide methacrylate, monoalkyl amide acrylate, and monoalkyl amide methacrylate. , Ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, third butyl (meth)acrylate, n-octyl (meth)acrylate, (meth) 2-ethylhexyl acrylate, n-dodecyl methacrylate, (meth)acrylic acid Alkyl (meth)acrylate such as stearyl ester, isostearyl (meth)acrylate, cyclic alkyl ester of (meth)acrylic acid such as cyclohexyl (meth)acrylate, (meth)acrylic acid 2 -Hydroxyalkyl (meth)acrylate such as hydroxyethyl, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (methyl) such as benzyl (meth)acrylate ) Aryl acrylate, methoxymethyl (meth)acrylate, methoxyethyl (meth)acrylate, alkoxyalkyl (meth)acrylate, vinyl acetate, vinyl pyrrolidone, styrene, α- Structural units derived from monomers such as methylstyrene and acrylonitrile. These monomers are almost available as commercial products.

<4> The copolymer of the present invention

The copolymer of the present invention is a copolymer containing the structural unit (a) and the structural unit (b) in its skeleton. In addition, the copolymer of the present invention is generally a random copolymer in which constituent units are randomly bonded, and may also be a block copolymer or a graft copolymer.

The copolymer of the present invention is characterized by a weight average molecular weight of 20,000 to 110,000. By setting the weight-average molecular weight to the aforementioned range, the copolymer of the present invention becomes elastic.

The weight average molecular weight of the copolymer of the present invention is preferably from 20,000 to 80,000, further preferably from 30,000 to 80,000, more preferably from 40,000 to 70,000, even more preferably from 50,000 to 70,000, and particularly preferably from 57,000 to 66000.

Here, the weight average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by GPC.

The method for producing the copolymer of the present invention is not particularly limited. For example, a monomer derived from each constituent unit may be used in a solvent It is mixed and obtained by a method of conducting a polymerization reaction according to a method generally used in the polymerization of acrylic monomers.

Here, by changing the reaction time or reaction temperature of the polymerization reaction, the weight average molecular weight of the copolymer can be adjusted. Specifically, by shortening the reaction time, the weight average molecular weight can be reduced.

In addition, when the copolymer of the present invention is used, water solubility is preferable from the viewpoint of ease of handling. The copolymer here is defined as a copolymer whose transmittance of a 20% by mass aqueous solution of the copolymer is at least 90% at 25°C. In order to obtain such a polymer, in the above-mentioned polymerization method, a polymerization method in which the aforementioned monomer mixture is subjected to radical polymerization in a mixed solvent of an aqueous solution and an aqueous solvent mixed with water at any ratio at 25° C. is particularly preferred. In addition, from the viewpoint that the amount of residual monomer after the polymerization reaction is small, the polymerization method using a buffer solution instead of water is particularly preferable. The buffering aqueous solution used in this method is not particularly limited as long as it is a commonly used buffer solution. Specifically, potassium chloride-hydrochloric acid solution, potassium hydrogen phthalate-hydrochloric acid solution, and dihydrogen phosphate can be exemplified. Potassium-disodium hydrogen phosphate solution, potassium hydrogen citrate-citric acid solution, sodium carbonate-sodium bicarbonate, etc. Alternatively, an aqueous solution of salts, acids, or alkalis that form a buffer solution with the ions of the initiator may be used to prepare a buffer solution at the time when the initiator is added. In addition, as the aqueous solvent used in this method, which is mixed with water at any ratio at 25°C, specifically, methanol, ethanol, n-propanol, isopropanol and the like having 1 to 3 carbon atoms, acetone, Ketones such as methyl ethyl ketone, glycols such as ethylene glycol, polyethylene glycol, propylene glycol, 1,3-butanediol, ethylene glycol monomethyl ether and ethylene glycol monoethyl ether Ether, tetrahydrofuran, etc. Among these aqueous solvents, from the viewpoint of easy polymerization reaction, alcohols having 1 to 3 carbon atoms such as methanol, ethanol, n-propanol, and isopropanol are particularly preferred.

In the present invention, the mass ratio of the structural unit (a) to the structural unit (b) constituting the copolymer is preferably 5:95-50:50, further preferably 10:90-45:55, and more preferably 20:80~40:60, especially good is 25:75~35:65.

Moreover, the molar ratio of the structural unit (a) and the structural unit (b) constituting the copolymer is preferably 8:92 to 62:38, further preferably 15:85 to 57:43, and more preferably 29: 71~52:48, especially good is 35:65~46:54.

By setting the mass ratio and the molar ratio of the structural unit (a) and the structural unit (b) of the copolymer to the aforementioned range, the elasticity can be further improved.

<5> Skin external preparation containing the copolymer of the present invention

The skin external preparation containing the copolymer of the present invention has an elastic feeling and is not liable to be sticky at the same time.

In the external preparation for skin, the content of the copolymer of the present invention is preferably 0.5 to 30% by mass, and more preferably 1 to 25% by mass.

As the external preparation for skin of the present invention, medicines, cosmetics, etc. other than ointment can be appropriately exemplified. Furthermore, as cosmetics, skin care products such as creams, lotions, lotions, beauty lotions, sunscreen cosmetics, foundations, foundations, eyeliners, mascaras, skin cleansers such as facial cleansers, hair tonics, etc. can be exemplified. Hair cosmetics such as hair styling lotion, styling spray, etc.

The external preparation for skin of the present invention can generally contain, as an optional component, a component used in the external preparation for skin, as long as the effect of the invention is not impaired. As this arbitrary component, specifically, Especially exemplified macadamia nut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower seed oil, cottonseed oil, jojoba oil, coconut oil, palm oil, liquid Lanolin, hardened coconut oil, hardened oil, wood wax, hardened castor oil, beeswax, candelilla wax, carnauba wax, insect wax, lanolin, reduced lanolin, hard lanolin, jojoba wax, etc. , Waxes, flowing paraffin, squalane, isooctadecane, ozokerite, paraffin, mineral wax, petrolatum, microcrystalline wax and other hydrocarbons, oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid , Higher fatty acids such as stearic acid, behenic acid, undecylenic acid, cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol, spermaceti Higher alcohols such as stearyl alcohol, cetyl isooctanoate, isopropyl myristate, cetyl isostearate, diisopropyl adipate, di-2-ethylhexyl sebacate, Cetyl lactate, diisostearyl malate, ethylene glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, glycerol di-2-heptyl undecanoate, tri-2- Synthetic ester oils such as glycerol ethylhexanoate, tri-2-ethylhexanoic acid, trimethylolpropane triisostearate, pentaerythritol tetra-2-ethylhexanoate, etc. Chain polysiloxane such as polysiloxane, methylphenyl polysiloxane, diphenyl polysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, twelve Cyclopolysiloxane such as methylcyclohexane silicone, amine-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane Anionic surfactants such as silicone oils such as modified polysiloxanes, fatty acid soaps (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, alkyl sulfate triethanolamine ether, etc. Cationic surfactants such as stearyl trimethylammonium chloride, xylylenediamine hydrochloride, lauryl amine oxide, and amphoteric interfacial activity of imidazoline series Agents (2-cocoyl-2-imidazolium hydroxide-1-carboxyethoxy 2 sodium salt, etc.), betaine surfactants (alkyl betaine, amide betaine, thiobetaine, etc. ), amphoteric surfactants such as acetylmethyl taurine, sorbitan fatty acid esters (sorbitan monostearate, sorbitan sesquioleate, etc.), glycerin Fatty acids (glycerol monostearate, etc.), fatty acid esters of propylene glycol (propylene glycol monostearate, etc.), hardened castor oil derivatives, POE sorbitan fatty acid esters (POE sorbitan monooleate , Monostearic acid polyoxyethylene sorbitan, etc.), POE sorbitol fatty acid esters (POE-sorbitol monolaurate, etc.), POE glycerol fatty acid esters (POE-glycerol monoiso Stearate, etc.), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyl dodecyl ether, etc.), POE alkyl phenyl ether (POE nonylphenyl ether, etc.), Pluronic type, POE‧POP alkyl ethers (POE‧POP2-decyltetradecyl ether, etc.), Tetronic, POE castor oil‧Hardening Castor oil derivatives (POE castor oil, POE hardened castor oil, etc.), nonionic surfactants such as sucrose fatty acid esters, alkyl glucoside, polyethylene glycol, glycerin, 1,3-butanediol , Erythritol, sorbitol, xylitol, maltitol, propylene glycol, dipropylene glycol, diglycerin, isopentyl glycol, 1,2-pentanediol, 2,4-hexanediol, 1, Moisture classification of polyhydric alcohols such as 2-hexanediol, 1,2-octanediol, sodium pyrrolidone carboxylate, lactic acid, sodium lactate, etc., Guanhua bean gum, quince seeds, carrageenan, galactopolymer Sugar, gum arabic, pectin, mannan, starch, three gums, cardlan gum, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methyl hydroxypropyl cellulose, cartilage sulfate Hormone, dermatan sulfate, glycogen, acetoheparin sulfate, hyaluronic acid, sodium hyaluronate, tragacanth gum, cutin sulfate Chondroitin, chondroitin, mucopolysaccharide sulfate, hydroxyethyl Guanhua bean gum, carboxymethyl Guanhua bean gum, dextran, keratan sulfate, locust bean gum, succinyl glycan, gentian acid, chitin, shell Thickeners such as polysaccharides, carboxymethyl chitin, agar, polyvinyl alcohol, polyvinylpyrrolidone, carbopol, sodium polyacrylate, polyethylene glycol, bentonite, etc., low grades of ethanol, isopropyl alcohol, etc. Alcohols, hexyl diethylaminohydroxybenzoyl benzoate, and third butyl methoxy benzoyl methane, p-aminobenzoic acid-based ultraviolet absorber, o-aminobenzoic acid-based ultraviolet absorber, water Salicylic acid-based ultraviolet absorbers, cinnamic acid-based ultraviolet absorbers and other ultraviolet absorbers, vitamin A or its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or its Vitamin B, α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, etc., vitamin E, vitamin D, vitamin H such as derivatives, vitamin B12, vitamin B15 or derivatives thereof , Pantothenic acid, pantethine, pyrroloquinoline quinone and other vitamins.

The external preparation for skin of the present invention can be prepared by treating the above-mentioned essential components and optional components by an ordinary method.

Moreover, the emulsified composition of the present invention that solves the second problem is characterized by including a water-soluble copolymer having a structural unit (c) derived from a hydrophobic monomer and a structural unit (d) derived from a hydrophilic monomer. In the following item <1>, water-soluble copolymers of hydrophobic monomers, hydrophilic monomers and copolymers of these will be described.

<1> Water-soluble copolymer [1] Hydrophobic monomer

In the present invention, a structural unit derived from the hydrophobic monomer represented by the general formula (1), (7) or (8) (hereinafter sometimes simply referred to as "constituent unit (7)" etc.) is used One or two or more of them are water-soluble copolymers contained as essential structural units.

Furthermore, in the present invention, "constituent unit derived from a monomer" refers to a structural unit formed by cleaving a carbon-carbon unsaturated bond possessed by a corresponding monomer by a polymerization reaction.

Hereinafter, the hydrophobic monomer represented by the general formula (1), (7) or (8) will be described.

(1-1) Hydrophobic monomer represented by general formula (7)

In the aforementioned general formula (7), R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁵ represents a branched hydrocarbon group having 13 to 30 carbon atoms that does not contain a ring structure, or 2 that does not contain a ring structure. More than 6 branched hydrocarbon groups with 6 to 12 carbon atoms.

Here, examples of the alkyl group represented by R ¹⁴ include methyl, ethyl, propyl, isopropyl, and cyclopropyl. In the present invention, R ¹⁴ is preferably a hydrogen atom or a methyl group.

In addition, as a branched hydrocarbon group having a ring structure of 13 to 30 carbon atoms represented by R ¹⁵ , 1-methyldodecyl, 11-methyldodecyl, 3-ethylundecyl, 3 -Ethyl-4,5,6-trimethyloctyl, 1-methyltridecyl, 1-hexyloctyl, 2-butyldecyl, 2-hexyloctyl, 4-ethyl-1- Isobutyloctyl, 1-methylpentadecyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 16-methylheptadecyl, 9-methylheptadecyl, 7-methyl-2-(3-methylhexyl)decyl, 3,7,11,15-tetra-methylhexadecyl, 2-octyldodecyl, 2-decyltetradecyl, 2 -Twelve bases and sixteen bases.

In addition, examples of the hydrocarbon group having 6 or more carbon atoms and having 2 or more branches not containing a ring structure represented by R ¹⁵ include 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1-dimethylpentyl, 1-isopropylbutyl, 1-isopropyl-2-methylpropyl, 1,1-diethylpropyl, 1-ethyl-1-isopropylpropyl, 2-ethyl-4-methylpentyl, 1- Propyl-2,2-dimethylpropyl, 1,1,2-trimethyl-pentyl, 1-isopropyl-3-methylbutyl, 1,2-dimethyl-1-ethyl Butyl, 1,3-dimethyl-1-ethylbutyl, 1-ethyl-1-isopropyl-propyl, 1,1-dimethylhexyl, 1-methyl-1-ethyl Amylpentyl, 1-methyl-1-propylbutyl, 1,4-dimethylhexyl, 1-ethyl-3-methylpentyl, 1,5-dimethylhexyl, 1-ethyl -6-methylheptyl, 1,1,3,3-tetramethylbutyl, 1,2-dimethyl-1-isopropylpropyl, 3-methyl-1-(2,2- Dimethylethyl)butyl, 1-isopropylhexyl, 3,5,5-trimethylhexyl, 2-isopropyl-5-methylhexyl, 1,5-dimethyl-1-ethyl Hexyl, 3,7-dimethyloctyl, 2,4,5-trimethylheptyl, 2,4,6-trimethylheptyl, 3,5-dimethyl-1-(2, 2-dimethylethyl)hexyl and so on.

(1-2) Hydrophobic monomer represented by general formula (1) or (8)

In the aforementioned general formulas (1) and (8), R ¹ and R ¹⁶ represent a hydrogen atom or a C 1-3 alkyl group, and R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different , And represents a branched C 6-22 acyl group that does not contain a ring structure. X represents a group that desorbs the OH group from the triol.

Here, examples of the alkyl group represented by R ¹ and R ¹⁶ include methyl, ethyl, propyl, isopropyl, and cyclopropyl. In the present invention, R ¹ is preferably hydrogen or methyl.

In addition, examples of R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ^{19 that} do not contain a ring structure and have branched C 6-22 acyl groups include 2-methylpentyl acyl and 3-methyl Pentylpentyl, 4-methylpentyl, 2-ethylbutyryl, 2-ethylbutyryl, 2,2-dimethylbutyryl, 3,3-dimethylbutyryl, 2-methylhexyl , 4-methylhexyl, 5-methylhexyl, 2,2-dimethylpentyl, 4,4-dimethylpentyl, 2-methylheptyl, 2-ethyl Hexyl, 2-propylpentyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentyl, 2-methyloctyl, 3,3,5-trimethyl Hexamyl, 2-methylnonyl, 4-methylnonyl, 8-methylnonyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2- Tert-butylhexyl, 2,2-diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methyldecyl, 2-methyl-2-ethyloctyl, 2-methylundecyl, 10-methylundecyl, 2,2-dimethyldecyl, 2-ethyldecyl, 2- Butyloctyl, diethyloctyl, 2-third butyl-2,2,4-trimethylpentyl, 10-methyldodecyl, 3-methyldodecyl, 4-methyl Yldodecyl, 11-methyldodecyl, 10-ethylundecyl, 12-methyltridecyl, 2-butyldecyl, 2-hexyloctyl, 2-butyl -2-ethyloctyl, 12-methyltetradecyl, 14-methylpentadecyl, 2-butyldodecyl, 2-hexyldecyl, 16-methylheptadecyl, 2,2-Dimethylhexyl, 2-butylhexadecyl, 2-hexyldodecyl, 2,4,10,14-tetramethylpentyl, 18-methyl nineteen amide Base, 3,7,11,15-tetra-methylhexadecyl, 19-methyleicosyl, etc.

Moreover, in a preferred embodiment of the present invention, in the general formulas (1) and (8), R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ¹⁹ may be the same or different, and have no ring structure A branched carbon group with a carbon number of 10 to 22, or a ring group with no more than 2 branches and a carbon group with a carbon number of 6 to 9.

As such a preferred embodiment, R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ^{19 which} do not contain a ring structure and have a branched C 10-22 acyl group may include 2-methylnonyl Group, 4-methylnonylyl group, 8-methylnonylyl group, 4-ethyloctylyl group, 2-ethyloctylyl group, 2-butylhexylyl group, 2-butylhexylyl group, 2-third butylhexylyl group, 2, 2-Diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methyldecyl, 2-methyl-2-ethyloctyl , 2-methylundecyl, 10-methylundecyl, 2,2-dimethyldecyl, 2-ethyldecyl, 2-butyloctyl, diethyloctyl, 2 -Third-butyl-2,2,4-trimethylpentylyl, 10-methyldodecyl, 3-methyldodecyl, 4-methyldodecyl, 11-methyl Dodecanoyl, 10-ethylundecyl, 12-methyltridecyl, 2-butyldecyl, 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-methyl Yltetradecyl, 14-methylpentadecyl, 2-butyldodecyl, 2-hexyldecyl, 16-methylheptadecyl, 2,2-dimethylhexyl , 2-butylhexadecyl, 2-hexyldodecyl, 2,4,10,14-tetramethylpentyl, 18-methyl nonadecyl, 3,7,11,15- Tetramethyl hexadecyl, 19-methyl eicosyl, etc.

In addition, as a preferred embodiment, an acyl group having 6 to 9 carbon atoms having 2 or more branches and not containing a ring structure represented by R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ¹⁹ can be exemplified by 2 ,2-dimethylbutyryl, 3,3-dimethylbutyryl, 2,2-dimethylpentyl, 4,4-dimethylpentyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentanyl, 3,5,5-trimethylhexyl, etc.

In the general formula (1), the group derived from triol represented by X is not particularly limited as long as it is a group from which the OH group is desorbed from the triol. A group exemplified by a trihydric alcohol selected from the group consisting of glycerin, trimethylolpropane, and trimethylolethane desorbs the OH group is suitably exemplified.

In addition, in the general formula (8), the group derived from a tetrahydric alcohol represented by Y is not particularly limited as long as it desorbs the OH group from the tetrahydric alcohol, and can be appropriately exemplified by The tetrahydric alcohol of the group of alcohol, pentaerythritol, erythritol, D-threitol, and L-threitol desorbs the OH group.

In the present invention, it is particularly preferable to use a water-soluble copolymer containing the structural unit (1).

Furthermore, in a more preferred embodiment of the present invention, the hydrophobic monomer represented by the general formula (1) is a hydrophobic monomer represented by the following general formula (15).

(In the general formula (15), R ²⁴ and R ²⁵ may be the same or different, and represent a branched carbon group having 16 to 22 carbon atoms that does not contain a ring structure. Z represents a OH group desorbed from a triol base).

The carbon number of the acyl group of R ²⁴ and R ^{25 in} the general formula (15) is 12-22, more preferably 14-20, and particularly preferably 16-20.

In addition, the carbon number of the main chain of the acyl group of R ²⁴ and R ^{25 in} the general formula (15) is preferably 9 to 21, more preferably 12 to 20, and particularly preferably 16 to 18.

In addition, the branch number of the acyl group of R ²⁴ and R ^{25 in} the general formula (15) is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

In addition, in the acyl group of R ²⁴ and R ²⁵ in the general formula (15), the larger the position number of the carbon of the main chain of the branch chain bonding, the better. Specifically, the branched chain is preferably bonded to the first to third carbons at the end of the autonomous chain, more preferably the first or second carbon, and particularly preferably the first carbon.

As R ²⁴ and R ²⁵ , specifically, 10-methyl undecyl group, 10-methyl dodecyl group, 11-methyl dodecyl group, 10-ethyl undecyl group, 12-Methyltridecyl, 12-methyltetradecyl, 14-methylpentadecyl, 16-methylheptadecyl, 2,4,10,14-tetramethylpentyl , 18-methyl nineteen amide, 3,7,11,15-tetra-methyl hexadecyl, 19-methyl eicosyl, etc.

In the general formula (15), the group derived from triol represented by Z is not particularly limited as long as it desorbs the OH group from the triol, and can be appropriately exemplified by a group selected from the group consisting of glycerol and triol. The trihydric alcohol of the group of methylolpropane and trimethylolethane desorbs the OH group.

[2] Hydrophilic monomer

As the hydrophilic monomer of the present invention, a polymerizable carboxylic acid and compounds represented by the general formula (2), the general formulas (9), (10), and (11) can be used.

(2-1) polymerizable carboxylic acid,

In the present invention, specific examples of the polymerizable carboxylic acid or its salt include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid and its sodium, potassium, ammonium, and amine salts. . Among these, acrylic acid, methacrylic acid, and their salts are particularly preferred from the viewpoint of high polymerizability. in When the water-soluble copolymer of the present invention is introduced into a structural unit derived from a polymerizable carboxylic acid salt, the polymerizable carboxylic acid may be prepared as a salt in advance to perform a polymerization reaction, or the polymerization reaction may be used to derive After derivation of the structural unit into a water-soluble copolymer, it is neutralized with an alkali to make a salt.

(2-2) Hydrophilic monomer represented by general formula (2)

In the aforementioned general formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁶ represents a hydrogen atom and a carbon atom having 6 to 6 carbon atoms The aromatic hydrocarbon group of 10, the aliphatic hydrocarbon group of 1 to 14 carbon atoms, or the acyl group of 1 to 12 carbon atoms. n represents an integer of 6~40.

Examples of the alkyl group represented by R ⁴ in the general formula (2) include methyl, ethyl, propyl, isopropyl, and cyclopropyl. In the present invention, R ⁴ is preferably a hydrogen atom or a methyl group.

In addition, as the alkylene group represented by R ⁵ , ethyl group, ethyl group, isopropyl group, 2-hydroxypropyl group, 2-hydroxy-2-methyl ethyl group, 2-hydroxy- 1-methylethylidene, etc., but among these, ethylidene or propylidene are preferred, and ethylidene is more preferred.

In addition, among the groups represented by R ⁶ , examples of the aromatic groups having 6 to 10 carbon atoms include phenyl, benzyl, tolyl, and ethylphenyl groups. As the aliphatic hydrocarbon groups having 1 to 14 carbon atoms, Appropriate examples include methyl, ethyl, butyl, tertiary butyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, lauryl, etc.; as a C 1-12 acyl group, a methyl acyl group can be appropriately exemplified. , Acetyl, propyl, butyl, isobutyl, pentyl, lauryl, etc. Among these, the group represented by R ^{5 is} preferably an aliphatic hydrocarbon group having 1 to 14 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.

Furthermore, n in the general formula (2) is in the range of 6 to 40.

Among the monomers represented by the general formula (2), as the monomer in which R ⁵ is propylene, specifically, polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, poly Propylene glycol (9) monomethacrylate, polypropylene glycol (13) monomethacrylate, etc. Furthermore, the number in parentheses indicates N. Most of these polymers are available as commercial products. Specific examples of these commercially available products include trade names "Blenmer" AP-400, AP-550, AP-800, PP-500, and PP-800 (all manufactured by Nippon Oil & Fats Co., Ltd.).

Among the monomers represented by the general formula (2), as the monomer in which R ⁵ is an ethylidene group, specifically, polyethylene glycol (10) monoacrylate, polyethylene glycol (8) monomer Methacrylate, polyethylene glycol (23) monoacrylate, polyethylene glycol (23) monomethacrylate, methoxypolyethylene glycol (9) acrylate, methoxypolyethylene glycol ( 9) Methacrylate, methoxypolyethylene glycol (23) methacrylate, oleyloxy polyethylene glycol (18) methacrylate, lauryloxy polyethylene glycol (18) acrylate, Lauryloxy polyethylene glycol (10) methacrylate, stearyl polyethylene glycol (30) monomethacrylate, etc.

The above-mentioned hydrophilic monomers can be obtained in a high yield by esterification reaction of corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride. In addition, since many commercial products already exist, the commercial products can also be used. As such a commercially available product, specifically, the trade names of Blenmer, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, and PSE-1300 (all of which are Japanese oil ) System) etc.

(2-3) Hydrophilic monomer represented by general formula (9)

As the hydrophilic monomer of the present invention, the hydrophilic monomer represented by the aforementioned general formula (9) can also be used.

Specific examples of the hydrophilic monomer represented by the general formula (9) include 2-acryloyloxyethyl phosphate choline (APC) and 2-methacryloyloxyethyl phosphate choline ( MPC). Such monomers can be synthesized by the following method described in Polymer Journal, Vol22, No. 5, for example.

<synthesis method>

Reacting 2-bromoethylphosphoryl dichloride with 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate to obtain 2-methacryloxyethyl-2'-bromoethyl phosphoric acid or 2- After acryloyloxyethyl-2'-bromoethyl phosphoric acid, these compounds are reacted with triethylamine in methanol.

(2-4) Hydrophilic monomer represented by general formula (10)

As the hydrophilic monomer of the present invention, the hydrophilic monomer represented by the general formula (10) can also be used.

Among the hydrophilic monomers represented by the general formula (10), the reducing sugar that is a group that removes hydrogen from the hydroxyl group at the 1-position of the reducing sugar represented by GO- can be specifically selected from the group consisting of glucose and mannose. Groups of monosaccharides such as sugar, galactose, arabinose, xylose, ribose, disaccharides such as maltose, lactose, cellobiose, trisaccharides such as maltotriose, and oligosaccharides such as maltooligosaccharide One or two or more, among which one or two or more selected from the group consisting of glucose, galactose, arabinose, xylose, ribose, maltose, lactose, and cellobiose is preferred, and glucose is particularly preferred. In addition, as the monomer represented by the general formula (10), methacrylic acid glucosyloxy Ethyl ester (hereinafter abbreviated as GEMA) or glucosyloxyethyl acrylate (hereinafter abbreviated as GEA) is preferred.

(2-5) Hydrophilic monomer represented by general formula (11)

As the hydrophilic monomer of the present invention, the hydrophilic monomer represented by the aforementioned general formula (11) can also be used.

In the monomer of the general formula (11), the amino acid as the amino acid residue represented by R ²³ is not particularly limited as long as it is a generally known amino acid, and specifically, glycine can be exemplified. Acid, alanine, glutamic acid, lysine, arginine, etc. Among these, since the skin barrier effect of the water-soluble copolymer obtained is good, ionic acid residues are particularly preferable.

In addition, the polyamine of the polyamine residue represented by R ²³ means an amine having two or more amine groups that can be substituted with an alkyl group in the same molecule. Specifically, a diamine, triamine, tetraamine or An amine in which the hydrogen atom of the amine group is substituted with an alkyl group. Among these, from the viewpoint of excellent use of skin external preparations containing the obtained water-soluble copolymer, diamine is preferable, and as a particularly preferable specific example, from the viewpoint of ease of obtaining raw materials at the time of synthesis, Examples include ethylenediamine, 1,4-diamino-n-butane, 1,6-diamino-n-hexane, and the like.

The amine alcohol as the amine alcohol residue represented by R ²³ means a compound having an alkyl-substituted amine group and an alcoholic hydroxyl group in the same molecule. The amino alcohol is not particularly limited as long as it is generally known, and specific examples include ethanolamine, triethylaminoethanol, and the like.

The salt of the monomer represented by the general formula (11) is not particularly limited, and specifically, there can be exemplified sodium salts, potassium salts, ammonium salts, amine salts and the like neutralized with an acid moiety, or Hydrochloric acid partially neutralized with acid Salt, sulfate, nitrate, phosphate, citrate, oxalate, carbonate, etc. When the water-soluble copolymer of the present invention is introduced into the structural unit derived from the monomer salt represented by the general formula (11), the monomer represented by the general formula (11) may be prepared as a salt in advance to perform a polymerization reaction, or Using a polymerization reaction, the structural unit derived from the monomer represented by the general formula (11) is derived as a water-soluble copolymer, and then neutralized to form a salt.

As specific examples of the monomer represented by the general formula (11) and salts thereof, compounds 1 to 11 having the following structure and salts thereof can be appropriately exemplified.

Compound 3

Compound 6

Compound 9

The hydrophilic monomer represented by the general formula (11), for example, as shown in the following reaction formulas (1) and (2), can be obtained by an esterification reaction using (meth)acrylic acid or (meth)acryloyl chloride , Amidation reaction synthesis.

(In the reaction formula, R ²² represents a hydrogen atom or a methyl group, and R ²³ represents an amino acid residue, a polyamine residue, or an amino alcohol residue. Q represents an oxygen atom or a group represented by NH).

As described above, in the present invention, as the hydrophilic polymer, the aforementioned general formula (2), the aforementioned general formula (9), the aforementioned general formula (10), and the aforementioned general formula (11) can be used.

In a preferred embodiment of the present invention, the water-soluble copolymer contains the structural unit (2) derived from the aforementioned general formula (2).

[3] Water-soluble copolymer

In the present invention, a water-soluble copolymer having a structural unit (1) and a structural unit (2) is particularly applicable. Furthermore, it is more preferable to use a water-soluble copolymer having a structural unit (15) and a structural unit (2).

Among such water-soluble copolymers, (methoxy methacrylate PEG-23/diisostearic acid glyceryl methacrylate) copolymer can be particularly preferably used.

By containing such a water-soluble copolymer, it can be an emulsified composition with low irritation, less stickiness, and excellent emulsification stability.

(Methoxy methacrylate PEG-23/diisostearic acid glyceryl methacrylate) copolymer, as the structural unit (c), is mainly contained from the hydrophobic monomer represented by the general formula (15), R ²⁴ and R ²⁵ are structural units (c) derived from a hydrophobic monomer of 16-methylheptadecyl group.

Moreover, as a structural unit (d), it is mainly comprised from the hydrophilic monomer represented by the said general formula (2), R ⁴ is a methyl group, R ⁵ is an ethyl group, R ⁶ is a methyl group, and n is 23 Structural unit (d) derived from a hydrophilic monomer.

Generally speaking, surfactants with high hydrophobicity are suitable for the formation of water-based emulsified compositions in oil, and conversely, surfactants with high hydrophilicity are suitable for the formation of oil-based emulsified compositions in water. The same applies to the water-soluble copolymer of the present invention. When the proportion of the hydrophobic constituent unit (c) is high, it is suitable for forming a water-based emulsified composition in oil, and the hydrophilic constituent unit (d) When the ratio is high, it is suitable for forming an oil-in-water emulsified composition.

As described above, the emulsified form of the formed emulsified composition can be adjusted by appropriately adjusting the ratio and ratio of the structural unit (c) and the structural unit (d).

In the present invention, the proportion of the constituent units (c) of the water-soluble copolymer in all constituent units is preferably 1 to 50% by mass, more preferably 20 to 50% by mass, and 30 to 40% by mass.

By setting the proportion of the structural unit (c) of the water-soluble copolymer within the aforementioned range, an oil-in-water emulsified composition with a further reduced stickiness can be provided.

In the present invention, the proportion of the constituent units (d) of the water-soluble copolymer in all constituent units is preferably 50 to 99% by mass, more preferably 50 to 80% by mass, and 60 to 70% by mass.

By setting the ratio of the structural unit (d) of the water-soluble copolymer to the aforementioned range, it is possible to provide an oil-in-water emulsified composition in which the stickiness is further reduced.

In the present invention, the mass ratio of the structural unit (c) and the structural unit (d) constituting the water-soluble copolymer is preferably 10:90-50:50, more preferably 20:80-50:50, and particularly preferably It is 30:70~40:60.

In addition, the molar ratio of the structural unit (c) and the structural unit (d) constituting the water-soluble copolymer is preferably 15:85 to 62:38, more preferably 29:71 to 62:38, and particularly preferably 41 : 59~52: 48.

By setting the mass ratio and the molar ratio of the structural unit (c) and structural unit (d) of the water-soluble copolymer to the aforementioned range, it can be a water-soluble copolymer with good emulsifying power suitable for forming an oil-in-water emulsion composition Thing.

In the present invention, the average molecular weight of the water-soluble copolymer is preferably from 20,000 to 110,000, further preferably from 20,000 to 80,000, more preferably from 30,000 to 80,000, even more preferably from 40,000 to 70,000, and particularly preferably from 50,000 to 70,000. Further particularly preferred is 57000~66000.

Here, the average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by GPC.

<2> Emulsified composition

The emulsified composition of the present invention is characterized in that it does not substantially contain an emulsifier other than the water-soluble copolymer.

Here, "substantially does not contain an emulsifier other than the above water-soluble copolymer" means that the content of the emulsifier other than the above water-soluble copolymer is 0.3% by mass or less, preferably 0.1% by mass or less, particularly preferably 0.01 Mass% or less, particularly preferably 0.001 mass% or less. In addition, emulsifiers other than the above water-soluble copolymer are particularly preferred.

The content of the water-soluble copolymer of the emulsified composition is preferably 0.1 to 50% by mass, and more preferably 0.5 to 30% by mass.

By setting the content of the water-soluble copolymer to the aforementioned range, the emulsification stability of the emulsified composition can be further improved.

The content of the water phase and the oil phase of the emulsified composition of the present invention can be appropriately adjusted by changing the ratio of the structural unit (c) and the structural unit (d) of the water-soluble copolymer.

The content of the oil phase and the water phase when using the water-soluble copolymer containing the structural unit (c) and the structural unit (d) in a ratio suitable for forming the above-mentioned oil-in-water emulsion composition will be described below.

In addition, in this specification, description is made as a case where the water-soluble copolymer of the present invention is not included in the oil phase and oil phase components, and the water phase and water phase components.

The content of the oil phase component of the emulsified composition of the present invention is preferably 0.01 to 80% by mass, more preferably 0.1 to 70% by mass.

By setting the content of the oil phase component to the aforementioned range, the emulsification stability of the emulsified composition can be improved.

In addition, the oil phase component is an oil agent and a lipophilic component, and refers to the component contained in the oil phase in the emulsified composition.

In the emulsified composition of the present invention, the mass ratio of the water-soluble copolymer to the oil phase component is preferably 1:100 to 1:0.2, and more preferably 1:70 to 1:0.3.

By setting the mass ratio of the water-soluble copolymer to the oil phase component to the aforementioned range, the emulsification stability of the emulsified composition can be improved.

In the emulsified composition of the present invention, the mass ratio of the oil phase to the water phase is preferably 0.1:99.9~80:20, more preferably 1:99~65:35.

By setting the mass ratio of the oil phase to the water phase to the aforementioned range, a stable oil-in-water emulsified composition can be formed.

The components contained in the oil phase and the water phase are not particularly limited.

Examples of the oil agent constituting the oil phase include liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, and silicone oils.

Examples of the liquid fats and oils include avocado oil, camellia oil, turtle oil, Australian walnut oil, corn oil, mink oil, olive oil, rapeseed oil, egg butter, sesame oil, apricot kernel oil, wheat germ oil, and camellia Oil, castor oil, linseed oil, safflower seed oil, cottonseed oil, perilla oil, white awn flower seed oil, soybean oil, peanut oil, bitter tea oil, Japanese cypress seed oil, rice bran oil, bougainvillea oil, Japanese tung oil, Dutch Jojoba oil, germ oil, triglycerin, trioctanoic acid glycerin, triisopalmitic acid glycerin, etc.

Examples of solid oils and fats include cocoa butter, coconut oil, horse fat, hardened coconut oil, palm oil, tallow, sheep fat, hardened tallow, palm kernel oil, lard, beef bone fat, wood wax kernel oil, hardened oil, Shea butter, wood wax, hardened castor oil, etc.

Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, insect wax, spermaceti wax, montan wax, bran wax, lanolin, kapok wax, lanolin acetate, and liquid Lanolin, sugarcane wax, isopropyl lanolin fatty acid, hexyl laurate, reduced lanolin, jojoba wax, rigid lanolin, shellac wax, POE lanolin alcohol, POE sheep Lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, etc.

Examples of the hydrocarbon oil include fluid paraffin, ozokerite, isooctadecane, paraffin, mineral wax, squalene, petrolatum, and microcrystalline wax.

Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid (behenic acid), 12-hydroxystearic acid, undecylenic acid, and tall oil acid ( tall oil acid) etc.

Examples of higher alcohols include cetyl alcohol, stearyl alcohol, behenyl alcohol, squalanol, myristyl alcohol, and cetearyl alcohol.

Examples of synthetic ester oils include isopropyl myristate, cetyl caprylate, octyl dodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, and myristate myristate. Ester, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, sucrose hard Fatty acid ester, sucrose oleate, cholesterol 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkanediol monoisostearate, didecane Neopentyl glycol acid, diisostearyl malate, glycerol di-2-heptyl undecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triiso Stearate, pentaerythritol tetra-2-ethylhexanoate, glycerol tri-2-ethylhexanoate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate , 2-ethylhexyl palmitate, glycerol trimyristate, tri-2-heptyl undecyl glyceride, castor oil fatty acid methyl ester, oleic oleate, cetearyl alcohol, glycerol acetate Ester, 2-heptyl undecyl palmitate, cetyl palmitate, diisobutyl adipate, N-lauryl-L-glutamic acid-2-octyl dodecyl ester, diadipate -2-heptyl eleven Ester, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisosebacate Propyl ester, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, etc.

Examples of the silicone oil include chain polysiloxanes such as dimethyl polysiloxane, methyl phenyl polysiloxane, methyl hydrogen polysiloxane, and decamethyl polysiloxane. Cyclic polysiloxane such as dodecyl polysiloxane, tetramethyl tetrahydropolysiloxane, etc.

One oil or two or more oils can be used.

唑、2,2’-羥基-5-甲苯基苯并三唑、2-(2’-羥基-5’-第三丁基辛苯基) 苯并三唑、2-(2’-羥基-5’-甲苯基)苯并三唑、二苄肼、二對甲氧苯甲醯基甲烷、4-甲氧基-4’-第三丁基二苯甲醯基甲烷、5-(3,3’二甲基-2-亞降冰片基)-3-戊-2-酮等之紫外線吸收劑；醯基肌胺酸(例如，月桂醯基肌胺酸鈉)、麩胱甘肽、檸檬酸、蘋果酸、酒石酸、乳酸等之有機酸；維他命A及其衍生物、維他命B6鹽酸鹽、維他命B6三棕櫚酸酯、維他命B6二辛酸酯、維他命B2及其衍生物、維他命B12、維他命B15及其衍生物等之維他命B類、α-生育酚、β-生育酚、γ-生育酚、維他命E乙酸酯等之維他命E類、維他命D類、維他命H、泛酸、泛硫乙胺、菸鹼酸醯胺、菸鹼酸苯甲酯等之維他命類；γ-榖維素、尿囊素、甘草酸(鹽)、甘草次酸及其衍生物、傳明酸及其衍生物〔作為傳明酸衍生物，傳明酸的二聚體(例如，鹽酸反式-4-(反式-胺甲基環己烷羰基)胺甲基環己烷羧酸等)、傳明酸與氫醌之酯(例如，反式-4-胺甲基環己烷羧酸4’-羥苯酯等)、傳明酸與龍膽酸之酯(例如，2-(反式-4-胺甲基環己基羰氧基)-5-羥基苯甲酸及其鹽等)、傳明酸的醯胺(例如，反式-4-胺甲基環己烷羧酸甲基醯胺及其鹽、反式-4-(P-甲氧基苯甲醯基)胺甲基環己烷羧酸及其鹽、反式-4-胍甲基環己烷羧酸及其鹽)〕、檜木醇、沒藥醇、大果桉醛、百里酚、肌醇、柴胡皂素、人參皂素、絲瓜皂素、無患子皂素等之皂素類、泛酸醇基乙醚、乙炔雌二醇、傳明酸、熊果素、千金藤素、胎盤素等之各種藥劑；羊蹄、苦參、日本萍蓬草、橙、鼠尾草、蓍、錦葵、當藥、麝香草、東當歸、雲杉、樺木、問荊、絲 瓜、七葉樹、虎耳草、兔菊、百合、魁蒿、芍藥、蘆薈、梔子、日本花柏等之植物的萃取物；色素；多孔質及/或吸水性的粉末(例如，由玉米或馬鈴薯等得到的澱粉類、矽酸酐、滑石、高嶺土、矽酸鋁鎂、海藻酸鈣等之粉末)；中和劑；防腐劑；香料；顏料等。 The emulsified composition of the present invention may be blended with any additional components that are usually blended in cosmetics as long as the effects of the present invention are not impaired. As such added components, for example, moisturizing agents such as polyethylene glycol, glycerin, 1,3-butanediol, erythritol, sorbitol, xylitol, and maltitol; ethanol, etc. Lower alcohols; antioxidants such as butylhydroxytoluene, tocopherol, phytic acid, etc.; antibacterial agents such as benzoic acid, salicylic acid, sorbic acid, alkyl p-hydroxybenzoate, hexachlorophenol; p-aminobenzoic acid (below (Abbreviated as "PABA"), PABA monoglyceride, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester, N,N-dimethyl PABA methyl ester, N,N -Dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, N,N-dimethyl PABA2-ethylhexyl ester and other benzoic acid type ultraviolet absorbers; high mintyl-N-acetyl acetyl group Ortho-aminobenzoic acid and other anthranilic acid-based ultraviolet absorbers; amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, salicylic acid Salicylic acid ultraviolet absorber such as benzyl methyl ester, p-isopropyl alcohol phenyl salicylate; octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisocinnamate Propyl ester, cinnamic acid ethyl-2,4-diisopropyl ester, cinnamic acid methyl-2,4-diisopropyl ester, cinnamic acid propyl-p-methoxy ester, cinnamic acid isopropyl-p- Methoxyester, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-cinnamate-p-methoxyester), 2-ethoxyethyl cinnamate- p-methoxy ester, cinnamic acid cyclohexyl-p-methoxy ester, cinnamic acid ethyl-α-cyano-β-phenyl ester, cinnamic acid 2-ethylhexyl-α-cyano-β-phenyl ester, Cinnamic acid glyceryl mono-2-ethylhexyl-di-p-methoxy ester and other cinnamic acid ultraviolet absorbers; cinnamic acid [3-bis (trimethylsiloxy) methylsilyl-1-methyl Propylpropyl]-3,4,5-trimethoxyester, cinnamic acid [3-bis(trimethylsiloxy)methylsilyl-3-methylpropyl]-3,4,5-trimethoxy Ester, cinnamic acid [3-bis(trimethylsiloxy)methylsilylpropyl]-3,4,5-trimethoxyester, cinnamic acid [3-bis(trimethylsiloxy)methyl Silylbutyl]-3,4,5-trimethoxyester, cinnamic acid [3-ginseng (trimethylsiloxy)silylbutyl]-3,4,5-trimethoxyester, cinnamic acid [3 -Ginseng(trimethylsiloxy)silylbutyl]-3,4,5-trimethoxyester, cinnamic acid[3-ginseng(trimethylsiloxy)silyl-1-methylpropyl] Silicone-based cinnamic acid ultraviolet absorbers such as -3,4-dimethoxyester; 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2 ,2'-Dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone Ketone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone , 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octyloxy Benzophenone-based ultraviolet absorbers such as benzophenone and 4-hydroxy-3-carboxybenzophenone; 3-(4'-methylbenzylidene)-d,l-camphor, 3-benzene Methylene-d,l-camphor, ethyl 4-imidazole acrylate, 2-phenyl-5-methylbenzo

Azole, 2,2'-hydroxy-5-tolylbenzotriazole, 2-(2'-hydroxy-5'-third butyloctylphenyl) benzotriazole, 2-(2'-hydroxy- 5'-tolyl) benzotriazole, dibenzhydrazine, di-p-methoxybenzyl methane, 4-methoxy-4'-third butyl dibenzoyl methane, 5-(3, 3'dimethyl-2-norbornyl)-3-pentan-2-one and other ultraviolet absorbers; acetylsarcosinate (for example, sodium lauryl sarcosinate), glutathione, lemon Organic acids such as acids, malic acid, tartaric acid, and lactic acid; vitamin A and its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 and its derivatives, vitamin B12, Vitamin B15 and its derivatives such as vitamin B, α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, etc. Vitamin E, vitamin D, vitamin H, pantothenic acid, pantethine Vitamins such as amine, niacinamide, benzyl nicotinate, etc.; γ-duoweisu, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid and its derivatives, tranexamic acid and its derivatives [As a tranexamic acid derivative, a dimer of tranexamic acid (for example, trans-4-hydrochloride (trans-aminomethylcyclohexanecarbonyl)aminemethylcyclohexanecarboxylic acid, etc.), tranexamic acid Esters with hydroquinone (for example, trans-4-aminomethylcyclohexanecarboxylic acid 4'-hydroxyphenyl ester, etc.), esters of tranexamic acid and gentisic acid (for example, 2-(trans-4- (Aminomethylcyclohexylcarbonyloxy)-5-hydroxybenzoic acid and its salts, etc.), tranexamic acid amide (for example, trans-4-amine methylcyclohexane carboxylic acid methyl amide and its salts) , Trans-4-(P-methoxybenzyl)aminomethylcyclohexanecarboxylic acid and its salts, trans-4-guanidinemethylcyclohexanecarboxylic acid and its salts)], cypressol , Myrrhol, eucalyptol, thymol, inositol, Bupleurum saponin, ginseng saponin, loofah saponin, saponin saponin, pantothenol alcohol ether, ethinyl estradiol Various medicaments such as methic acid, arbutin, erythrophyllin, placenta, etc.; sheep's hoof, Sophora flavescens, Japanese wing grass, orange, sage, yarrow, mallow, Chinese medicine, thyme, angelica, spruce, birch , Hydrangea, loofah, horse chestnut, saxifrage, rabbit chrysanthemum, lily, sagebrush, peony, aloe, gardenia, Japanese cypress and other plant extracts; pigment; porous and/or water-absorbing powder (For example, powders of starches, silicic anhydride, talc, kaolin, magnesium aluminum silicate, calcium alginate, etc. obtained from corn or potatoes, etc.; neutralizers; preservatives; spices; pigments, etc.

The emulsified composition of the present invention can be produced by separately preparing an aqueous phase component and an oil phase component including the above-mentioned water-soluble copolymer, and stirring and mixing these by a conventional method.

The emulsified composition of the present invention is low in irritation and is preferably used as cosmetics, skin external preparations, quasi-medicinal products, or pharmaceutical products such as emulsions, creams, cosmetic liquids, sunscreens, liquid foundations, etc. from the viewpoint of less stickiness.

<3> emulsifier

The present invention also relates to an emulsifier containing the above water-soluble copolymer. The descriptions related to the above water-soluble copolymer and emulsified composition can be applied to the emulsifier of the present invention.

<4> Manufacturing method of emulsified composition

The present invention also relates to a method for producing an emulsified composition using the emulsifier of the present invention described above. The method of the present invention is characterized in that an emulsifier other than the emulsifier of the present invention is not used. The descriptions related to the above water-soluble copolymer and emulsified composition can be applied to the production method of the present invention.

The skin cleansing agent of the present invention that solves the third and fourth problems is characterized by including a water-soluble copolymer having a structural unit (e) derived from a hydrophobic monomer and a structural unit (f) derived from a hydrophilic monomer. In the following item <1>, water-soluble copolymers of hydrophobic monomers, hydrophilic monomers and copolymers of these will be described.

<1> Water-soluble copolymer [1] Hydrophobic monomer

In the present invention, a structural unit derived from the hydrophobic monomer represented by the general formula (1), (7) or (8) (hereinafter sometimes simply referred to as "constituent unit (7)" etc.) is used One or two or more of them are water-soluble copolymers contained as essential structural units.

Furthermore, in the present invention, "constituent unit derived from a monomer" refers to a constituent unit formed by cleaving a carbon-carbon unsaturated bond possessed by the corresponding monomer by a polymerization reaction.

Hereinafter, the hydrophobic monomer represented by the general formula (1), (7) or (8) will be described.

(1-1) Hydrophobic monomer represented by general formula (7)

In the aforementioned general formula (7), R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁵ represents a branched hydrocarbon group having 13 to 30 carbon atoms that does not contain a ring structure, or 2 that does not contain a ring structure. More than 6 branched hydrocarbon groups with 6 to 12 carbon atoms.

Here, examples of the alkyl group represented by R ¹⁴ include methyl, ethyl, propyl, isopropyl, and cyclopropyl. In the present invention, R ¹⁴ is preferably a hydrogen atom or a methyl group.

In addition, as a branched hydrocarbon group having a ring structure of 13 to 30 carbon atoms represented by R ¹⁵ , 1-methyldodecyl, 11-methyldodecyl, 3-ethylundecyl, 3 -Ethyl-4,5,6-trimethyloctyl, 1-methyltridecyl, 1-hexyloctyl, 2-butyldecyl, 2-hexyloctyl, 4-ethyl-1- Isobutyloctyl, 1-methylpentadecyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 16-methylheptadecyl, 9-methylheptadecyl, 7-methyl-2-(3-methylhexyl)decyl, 3,7,11,15-tetra-methylhexadecyl, 2-octyldodecyl, 2-decyltetradecyl, 2 -Twelve bases and sixteen bases.

In addition, examples of the hydrocarbon group having 6 or more carbon atoms and having 2 or more branches not containing a ring structure represented by R ¹⁵ include 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1-dimethylpentyl, 1-isopropylbutyl, 1-isopropyl-2-methylpropyl, 1,1-diethylpropyl, 1-ethyl-1-isopropylpropyl, 2-ethyl-4-methylpentyl, 1- Propyl-2,2-dimethylpropyl, 1,1,2-trimethyl-pentyl, 1-isopropyl-3-methylbutyl, 1,2-dimethyl-1-ethyl Butyl, 1,3-dimethyl-1-ethylbutyl, 1-ethyl-1-isopropyl-propyl, 1,1-dimethylhexyl, 1-methyl-1-ethyl Amylpentyl, 1-methyl-1-propylbutyl, 1,4-dimethylhexyl, 1-ethyl-3-methylpentyl, 1,5-dimethylhexyl, 1-ethyl -6-methylheptyl, 1,1,3,3-tetramethylbutyl, 1,2-dimethyl-1-isopropylpropyl, 3-methyl-1-(2,2- Dimethylethyl)butyl, 1-isopropylhexyl, 3,5,5-trimethylhexyl, 2-isopropyl-5-methylhexyl, 1,5-dimethyl-1-ethyl Hexyl, 3,7-dimethyloctyl, 2,4,5-trimethylheptyl, 2,4,6-trimethylheptyl, 3,5-dimethyl-1-(2, 2-dimethylethyl)hexyl and so on.

(1-2) Hydrophobic monomer represented by general formula (1) or (8)

In the aforementioned general formulas (1) and (8), R ¹ and R ¹⁶ represent a hydrogen atom or a C 1-3 alkyl group, and R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different , And represents a branched C 6-22 acyl group that does not contain a ring structure. X represents a group that desorbs the OH group from the triol.

Here, examples of the alkyl group represented by R ¹ and R ¹⁶ include methyl, ethyl, propyl, isopropyl, and cyclopropyl. In the present invention, R ¹ is preferably hydrogen or methyl.

In addition, examples of R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ^{19 that} do not contain a ring structure and have branched C 6-22 acyl groups include 2-methylpentyl acyl and 3-methyl Pentylpentyl, 4-methylpentyl, 2-ethylbutyryl, 2-ethylbutyryl, 2,2-dimethylbutyryl, 3,3-dimethylbutyryl, 2-methylhexyl , 4-methylhexyl, 5-methylhexyl, 2,2-dimethylpentyl, 4,4-dimethylpentyl, 2-methylheptyl, 2-ethyl Hexyl, 2-propylpentyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentyl, 2-methyloctyl, 3,3,5-trimethyl Hexamyl, 2-methylnonyl, 4-methylnonyl, 8-methylnonyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2- Tert-butylhexyl, 2,2-diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methyldecyl, 2-methyl-2-ethyloctyl, 2-methylundecyl, 10-methylundecyl, 2,2-dimethyldecyl, 2-ethyldecyl, 2- Butyloctyl, diethyloctyl, 2-third butyl-2,2,4-trimethylpentyl, 10-methyldodecyl, 3-methyldodecyl, 4-methyl Yldodecyl, 11-methyldodecyl, 10-ethylundecyl, 12-methyltridecyl, 2-butyldecyl, 2-hexyloctyl, 2-butyl -2-ethyloctyl, 12-methyltetradecyl, 14-methylpentadecyl, 2-butyldodecyl, 2-hexyldecyl, 16-methylheptadecyl, 2,2-Dimethylhexyl, 2-butylhexadecyl, 2-hexyldodecyl, 2,4,10,14-tetramethylpentyl, 18-methyl nineteen amide Base, 3,7,11,15-tetra-methylhexadecyl, 19-methyleicosyl, etc.

Moreover, in a preferred embodiment of the present invention, in the general formulas (1) and (8), R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ¹⁹ may be the same or different, and have no ring structure A branched carbon group with a carbon number of 10 to 22, or a ring group with no more than 2 branches and a carbon group with a carbon number of 6 to 9.

As such a preferred embodiment, R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ^{19 which} do not contain a ring structure and have a branched C 10-22 acyl group may include 2-methylnonyl Group, 4-methylnonylyl group, 8-methylnonylyl group, 4-ethyloctylyl group, 2-ethyloctylyl group, 2-butylhexylyl group, 2-butylhexylyl group, 2-third butylhexylyl group, 2, 2-Diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methyldecyl, 2-methyl-2-ethyloctyl , 2-methylundecyl, 10-methylundecyl, 2,2-dimethyldecyl, 2-ethyldecyl, 2-butyloctyl, diethyloctyl, 2 -Third-butyl-2,2,4-trimethylpentylyl, 10-methyldodecyl, 3-methyldodecyl, 4-methyldodecyl, 11-methyl Dodecanoyl, 10-ethylundecyl, 12-methyltridecyl, 2-butyldecyl, 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-methyl Yltetradecyl, 14-methylpentadecyl, 2-butyldodecyl, 2-hexyldecyl, 16-methylheptadecyl, 2,2-dimethylhexyl , 2-butylhexadecyl, 2-hexyldodecyl, 2,4,10,14-tetramethylpentyl, 18-methyl nonadecyl, 3,7,11,15- Tetramethyl hexadecyl, 19-methyl eicosyl, etc.

In addition, as a preferred embodiment, an acyl group having 6 to 9 carbon atoms having 2 or more branches and not containing a ring structure represented by R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ¹⁹ can be exemplified by 2 ,2-dimethylbutyryl, 3,3-dimethylbutyryl, 2,2-dimethylpentyl, 4,4-dimethylpentyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentanyl, 3,5,5-trimethylhexyl, etc.

In the general formula (1), the group derived from triol represented by X is not particularly limited as long as it is a group from which the OH group is desorbed from the triol. A group exemplified by a trihydric alcohol selected from the group consisting of glycerin, trimethylolpropane, and trimethylolethane desorbs the OH group is suitably exemplified.

In addition, in the general formula (8), the group derived from a tetrahydric alcohol represented by Y is not particularly limited as long as it desorbs the OH group from the tetrahydric alcohol, and can be appropriately exemplified by The tetrahydric alcohol of the group of alcohol, pentaerythritol, erythritol, D-threitol, and L-threitol desorbs the OH group.

In the present invention, it is particularly preferable to use a water-soluble copolymer containing the structural unit (1).

In a more preferred embodiment of the present invention, the hydrophobic monomer represented by the general formula (1) is the hydrophobic monomer represented by the general formula (15).

The carbon number of the acyl group of R ²⁴ and R ^{25 in} the general formula (15) is 12-22, more preferably 14-20, and particularly preferably 16-20.

In addition, the carbon number of the main chain of the acyl group of R ²⁴ and R ^{25 in} the general formula (15) is preferably 9 to 21, more preferably 12 to 20, and particularly preferably 16 to 18.

In addition, the branch number of the acyl group of R ²⁴ and R ^{25 in} the general formula (15) is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

In addition, in the acyl group of R ²⁴ and R ²⁵ in the general formula (15), the larger the position number of the carbon of the main chain of the branch chain bonding, the better. Specifically, the branched chain is preferably bonded to the first to third carbons at the end of the autonomous chain, more preferably the first or second carbon, and particularly preferably the first carbon.

As R ²⁴ and R ²⁵ , specifically, 10-methyl undecyl group, 10-methyl dodecyl group, 11-methyl dodecyl group, 10-ethyl undecyl group, 12-Methyltridecyl, 12-methyltetradecyl, 14-methylpentadecyl, 16-methylheptadecyl, 2,4,10,14-tetramethylpentyl , 18-methyl nineteen amide, 3,7,11,15-tetra-methyl hexadecyl, 19-methyl eicosyl, etc.

In the general formula (15), the group derived from triol represented by Z is not particularly limited as long as it desorbs the OH group from the triol, and can be appropriately exemplified by a group selected from the group consisting of glycerol and triol. The trihydric alcohol of the group of methylolpropane and trimethylolethane desorbs the OH group.

[2] Hydrophilic monomer

As the hydrophilic monomer of the present invention, a polymerizable carboxylic acid and compounds represented by the aforementioned general formulas (2), (9), (10), and (11) can be used.

(2-1) Polymerizable carboxylic acid

In the present invention, specific examples of the polymerizable carboxylic acid or its salt include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid and its sodium, potassium, ammonium, and amine salts. . Among these, acrylic acid, methacrylic acid, and their salts are particularly preferred from the viewpoint of high polymerizability. When the water-soluble copolymer of the present invention is introduced into a structural unit derived from a polymerizable carboxylate, the polymerizable carboxylic acid may be prepared as a salt in advance to perform a polymerization reaction, or the polymerization reaction may be used to derive the self-polymerizable carboxylic acid After the constituent units are derived into water-soluble copolymers, they are made into salts by neutralization with alkali.

(2-2) Hydrophilic monomer represented by general formula (2)

In the aforementioned general formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁶ represents a hydrogen atom and a carbon atom having 6 to 6 carbon atoms The aromatic hydrocarbon group of 10, the aliphatic hydrocarbon group of 1 to 14 carbon atoms, or the acyl group of 1 to 12 carbon atoms. n represents an integer of 6~40.

Examples of the alkyl group represented by R ⁴ in the general formula (2) include methyl, ethyl, propyl, isopropyl, and cyclopropyl. In the present invention, R ⁴ is preferably a hydrogen atom or a methyl group.

In addition, as the alkylene group represented by R ⁵ , ethyl group, ethyl group, isopropyl group, 2-hydroxypropyl group, 2-hydroxy-2-methyl ethyl group, 2-hydroxy- 1-methylethylidene, etc., but among these, ethylidene or propylidene are preferred, and ethylidene is more preferred.

In addition, among the groups represented by R ⁶ , examples of the aromatic groups having 6 to 10 carbon atoms include phenyl, benzyl, tolyl, and ethylphenyl groups. As the aliphatic hydrocarbon groups having 1 to 14 carbon atoms, Appropriate examples include methyl, ethyl, butyl, tertiary butyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, lauryl, etc.; as a C 1-12 acyl group, a methyl acyl group can be appropriately exemplified. , Acetyl, propyl, butyl, isobutyl, pentyl, lauryl, etc. Among these, the group represented by R ^{5 is} preferably an aliphatic hydrocarbon group having 1 to 14 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.

Furthermore, n in the general formula (2) is in the range of 6 to 40.

Among the monomers represented by the general formula (2), as the monomer in which R ⁵ is propylene, specifically, polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, poly Propylene glycol (9) monomethacrylate, polypropylene glycol (13) monomethacrylate, etc. Furthermore, the number in parentheses indicates N. Most of these polymers are available as commercial products. Specific examples of these commercially available products include trade names "Blenmer" AP-400, AP-550, AP-800, PP-500, and PP-800 (all manufactured by Nippon Oil & Fats Co., Ltd.).

Among the monomers represented by the general formula (2), as the monomer in which R ⁵ is an ethylidene group, specifically, polyethylene glycol (10) monoacrylate, polyethylene glycol (8) monomer Methacrylate, polyethylene glycol (23) monoacrylate, polyethylene glycol (23) monomethacrylate, methoxypolyethylene glycol (9) acrylate, methoxypolyethylene glycol ( 9) Methacrylate, methoxy polyethylene glycol (23) methacrylate, oleyloxy polyethylene glycol (18) methacrylate, lauryloxy polyethylene glycol (18) acrylate, Lauryloxy polyethylene glycol (10) methacrylate, stearyl polyethylene glycol (30) monomethacrylate, etc.

The above-mentioned hydrophilic monomers can be obtained in a high yield by esterification reaction of corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride. In addition, since many commercial products already exist, the commercial products can also be used. As such a commercially available product, specifically, the trade names of Blenmer, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, and PSE-1300 (all of which are Japanese oil ) System) etc.

(2-3) Hydrophilic monomer represented by general formula (9)

As the hydrophilic monomer of the present invention, the hydrophilic monomer represented by the aforementioned general formula (9) can also be used.

Specific examples of the hydrophilic monomer represented by the general formula (9) include 2-acryloyloxyethyl phosphate choline (APC) and 2-methacryloyloxyethyl phosphate choline ( MPC). Such monomers can be synthesized by the following method described in Polymer Journal, Vol22, No. 5, for example.

<synthesis method>

Reacting 2-bromoethylphosphoryl dichloride with 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate to obtain 2-methacryloxyethyl-2'-bromoethyl phosphoric acid or 2- After acryloyloxyethyl-2'-bromoethyl phosphoric acid, these compounds are reacted with triethylamine in methanol.

(2-4) Hydrophilic monomer represented by general formula (10)

As the hydrophilic monomer of the present invention, the hydrophilic monomer represented by the general formula (10) can also be used.

Among the hydrophilic monomers represented by the general formula (10), the reducing sugar that is a group that removes hydrogen from the hydroxyl group at the 1-position of the reducing sugar represented by GO- can be specifically selected from the group consisting of glucose and mannose. Groups of monosaccharides such as sugar, galactose, arabinose, xylose, ribose, disaccharides such as maltose, lactose, cellobiose, trisaccharides such as maltotriose, and oligosaccharides such as maltooligosaccharide One or two or more, among which one or two or more selected from the group consisting of glucose, galactose, arabinose, xylose, ribose, maltose, lactose, and cellobiose is preferred, and glucose is particularly preferred. Further, as the monomer represented by the general formula (10), glucosyloxyethyl methacrylate (hereinafter abbreviated as GEMA) or glucosyloxyethyl acrylate (hereinafter abbreviated as GEA) is preferred.

In the monomer of the general formula (11), the amino acid as the amino acid residue represented by R ²³ is not particularly limited as long as it is a generally known amino acid, and specifically, glycine can be exemplified. Acid, alanine, glutamic acid, lysine, arginine, etc. Among these, since the skin barrier effect of the water-soluble copolymer obtained is good, ionic acid residues are particularly preferable.

In addition, the polyamine of the polyamine residue represented by R ²³ means an amine having two or more amine groups that can be substituted with an alkyl group in the same molecule. Specifically, a diamine, triamine, tetraamine or An amine in which the hydrogen atom of the amine group is substituted with an alkyl group. Among these, from the viewpoint of excellent use of skin external preparations containing the obtained water-soluble copolymer, diamine is preferable, and as a particularly preferable specific example, from the viewpoint of ease of obtaining raw materials at the time of synthesis, Examples include ethylenediamine, 1,4-diamino-n-butane, 1,6-diamino-n-hexane, and the like.

The amine alcohol as the amine alcohol residue represented by R ²³ means a compound having an alkyl-substituted amine group and an alcoholic hydroxyl group in the same molecule. The amino alcohol is not particularly limited as long as it is generally known, and specific examples include ethanolamine, triethylaminoethanol, and the like.

The salt of the monomer represented by the general formula (11) is not particularly limited, and specifically, there can be exemplified sodium salts, potassium salts, ammonium salts, amine salts and the like neutralized with an acid moiety, or Partially acid neutralized hydrochloride, sulfate, nitrate, phosphate, citrate, oxalate, carbonate, etc. When the water-soluble copolymer of the present invention is introduced into the structural unit derived from the monomer salt represented by the general formula (11), the monomer represented by the general formula (11) may be prepared as a salt in advance to perform a polymerization reaction, or Using a polymerization reaction, the structural unit derived from the monomer represented by the general formula (11) is derived as a water-soluble copolymer, and then neutralized to form a salt.

As specific examples of the monomer represented by the general formula (11) and salts thereof, the above-mentioned compounds 1 to 11 and salts thereof can be appropriately exemplified.

The hydrophilic monomer represented by the general formula (11), for example, as shown in the aforementioned reaction formulas (1) and (2), can be obtained by an esterification reaction using (meth)acrylic acid or (meth)acryloyl chloride , Amidation reaction synthesis.

As described above, in the present invention, as the hydrophilic polymer, the aforementioned general formula (2), the aforementioned general formula (9), the aforementioned general formula (10), and the aforementioned general formula (11) can be used.

In a preferred embodiment of the present invention, the water-soluble copolymer contains the structural unit (2) derived from the aforementioned general formula (2).

[3] Water-soluble copolymer

In the present invention, a water-soluble copolymer having a structural unit (1) and a structural unit (2) is particularly applicable. Furthermore, it is more preferable to use a water-soluble copolymer having a structural unit (15) and a structural unit (2).

Among such water-soluble copolymers, (methoxy methacrylate PEG-23/diisostearic acid glyceryl methacrylate) copolymer can be particularly preferably used.

By containing such a water-soluble copolymer, it is possible to provide a skin cleanser with less tightness after use.

(Methoxy methacrylate PEG-23/diisostearic acid glyceryl methacrylate) copolymer, as the structural unit (e), is mainly contained in the hydrophobic monomer represented by the general formula (15), R ²⁴ and R ²⁵ are structural units (e) derived from a hydrophobic monomer of 16-methylheptadecyl group.

Moreover, as a structural unit (f), it is mainly comprised from the hydrophilic monomer represented by the said general formula (2), R ⁴ is a methyl group, R ⁵ is an ethyl group, R ⁶ is a methyl group, and n is 23 Structural unit (f) derived from a hydrophilic monomer.

In the present invention, the proportion of the structural units (e) of the water-soluble copolymer in all the structural units is preferably 1 to 60% by mass, more preferably 10 to 50% by mass, and 20 to 40% by mass.

By setting the proportion of the structural unit (e) of the water-soluble copolymer within the aforementioned range, it is possible to provide a skin cleanser with a further reduced feeling of tightness after use.

In the present invention, the proportion of the constituent units (f) of the water-soluble copolymer in all constituent units is preferably 40 to 99% by mass, more preferably 50 to 90% by mass, and 60 to 80% by mass.

By setting the proportion of the structural unit (f) of the water-soluble copolymer within the aforementioned range, it is possible to provide a skin cleanser with a further reduced feeling of tightness after use.

In the present invention, the mass ratio of the constituent unit (e) and the constituent unit (f) constituting the water-soluble copolymer is preferably 1:99-60:40, more preferably 10:90-50:50, and particularly preferably It is 20:80~40:60.

In addition, the molar ratio of the structural unit (e) and the structural unit (f) constituting the water-soluble copolymer is preferably 1:99 to 71:29, further preferably 15:85 to 62:38, and more preferably 29:71~52:48, especially good is 35:65~45:55.

By setting the mass ratio and the molar ratio of the structural unit (e) and the structural unit (f) of the water-soluble copolymer to the aforementioned range, it is possible to obtain a water-soluble copolymer having a better effect of reducing tightness.

In the present invention, the average molecular weight of the water-soluble copolymer is preferably from 20,000 to 110,000, further preferably from 20,000 to 80,000, more preferably from 30,000 to 80,000, even more preferably from 40,000 to 70,000, and particularly preferably from 50,000 to 70,000. Further particularly preferred is 57000~66000.

Here, the average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by GPC.

<2> skin cleanser [1] Formulation

A skin cleanser refers to a composition containing cleansing ingredients, and is used for the purpose of washing away skin dirt such as sebum. As mentioned above, the skin cleanser has the effect of washing away the sebum present in the skin, and therefore has the problem of producing a tight feeling on the skin after use.

The skin cleanser of the present invention is characterized by containing the above water-soluble copolymer. According to the present invention, the cleansing power originally possessed by the skin cleanser is not hindered, or the cleansing power of the skin after use can be reduced while enhancing the cleansing power.

The dosage form of the skin cleansing agent of the present invention is not particularly limited as long as it is a dosage form generally used for skin cleansing agents, and can be applied. Common skin cleansers include solid, powder, cream, liquid, and gel skin cleansers, etc., and any of the dosage forms can be applied in the present invention.

The content of the above-mentioned water-soluble copolymer of the skin cleansing agent whose liquid form is cream, liquid, gel, etc. is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and particularly preferably 1 ~3% by mass.

By setting the content of the above-mentioned water-soluble copolymer to the aforementioned range, the cleansing power originally possessed by the skin cleanser will not be hindered, and the tightness of the skin after use can be further reduced.

Skin cleansers can be divided into a foaming type and a non-foaming type. Even if the invention is applied to any type of skin cleanser, it will not hinder the original cleansing power of the skin cleanser, and can reduce the tightness of the skin after use.

In the foaming and use type skin cleansing agent, from the viewpoint of improving the foamability, the content of the water-soluble copolymer is 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 0.8% by mass % Or more, especially good is more than 1% by mass.

In addition, from the viewpoint of reducing the stickiness of the skin after use, the content of the water-soluble copolymer is preferably 20% by mass or less, and more preferably 10% by mass or less, more preferably 3% by mass or less, and particularly preferably 1% by mass or less.

As a foaming skin cleanser, a cream-like skin cleanser is particularly mentioned.

In the non-foaming type skin cleansing agent, the content of the water-soluble copolymer is preferably 0.1 to 10% by mass, and more preferably 0.5 to 5 from the viewpoint of improving the ease of extension to the skin %, more preferably 0.6 to 3% by mass, and particularly preferably 0.7 to 2% by mass.

As a non-foaming type skin cleanser, a gel-like skin cleanser is particularly exemplified.

(2) Skin cleanser containing surfactant

A skin cleanser containing a surfactant as a cleaning ingredient has a strong cleaning power. On the other hand, it has a problem of a strong feeling of tightness of the skin after use. Therefore, it is preferable to apply the present invention to skin cleansers containing surfactants.

The surfactant that can be contained in the skin cleansing agent of the present invention is not particularly limited as long as it is generally used in skin cleansing agents, and any of ionic surfactants and nonionic surfactants can be used.

As the ionic surfactant, any of anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants can be used.

As anionic surfactants, specific examples include fatty acid soaps such as sodium fatty acid, potassium fatty acid, and fatty acid triethanolamine, sodium lauryl sulfate, potassium lauryl sulfate, which may have polyoxyethylene Triethanolamine such as lauryl sulfate can have polyoxyethylene alkyl sulfate salt, sodium lauryl phosphate can have polyoxyethylene, potassium lauryl phosphate, triethanolamine lauryl etc. can have polyoxyethylene Alkyl phosphate ester salts, alkyl sulfosuccinate salts, etc.

As anionic surfactants, particularly exemplified examples include alkyl trimethyl ammonium salt, alkyl pyridine salt, distearyl dimethyl ammonium chloride, dialkyl dimethyl ammonium salt, and poly(N, N'-dimethyl-3,5-methylenepiperidine), alkyl quaternary ammonium salt, alkyl dimethyl benzyl ammonium salt, alkyl isoquinoline salt, dialkyl morpholine salt, POE-alkylamine, alkylamine salt, polyamine fatty acid derivative, pentanol fatty acid derivative, xylylenediamine chloride, benzethonium chloride, etc.

Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants and betaine-based surfactants.

As the nonionic surfactant, glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan Fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene lanolin. Lanolin alcohol. Beeswax derivatives, polyoxyethylene castor oil. Hardened castor oil, polyoxyethylene sterol. Hydrogenated sterol, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene ether, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether fatty acid ester, polyoxyethylene hardened castor oil fatty acid ester, polyoxyethylene trihydroxy Methyl propane fatty acid ester, polyethylene glycol fatty acid ester, sucrose fatty acid ester, polyoxyethylene polyoxypropylene block copolymer, organically modified silicone, etc.

The content of these surfactants is not particularly limited, and can be appropriately set according to the type of surfactant.

Hereinafter, the skin cleansing agent containing the form of fatty acid soap, the form containing the nonionic surfactant, and the gel-like form will be described more specifically.

(2-1) Skin cleanser containing fatty acid soap

The invention is applied to a skin cleanser containing fatty acid soaps, without compromising the good foaming and dense foam quality of the skin cleanser, and can reduce the tightness of the skin after use.

The form of the skin cleanser containing fatty acid soap may be any of solid, liquid, and cream, but the liquid or cream is preferred. In particular, the form of cream-like skin cleansers used for foaming is preferred.

The fatty acid constituting the fatty acid soap is not particularly limited as long as it can be applied to skin cleansers, and it may be either saturated or unsaturated. The carbon number is 8 to 24, and particularly 10 to 22 is preferred. Specific examples of preferred ones include lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, hydroxystearic acid, hydroxydecenoic acid, coconut oil fatty acid, reduced coconut oil Fatty acids, tallow fatty acids, reduced tallow fatty acids, palm kernel fatty acids, etc. Among these fatty acids, one or more selected from the group consisting of myristic acid, palmitic acid, and stearic acid is preferred from the standpoint of foamability, safety, and stability. In particular, myristic acid and Three types of palmitic acid and stearic acid are preferred. Examples of the alkaline agent for forming such higher fatty acids and salts include alkali metal salts such as sodium and potassium, ammonium salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, and 2-amino groups. Alkanolamine salts such as 2-methylpropanol and 2-amino-2-methylpropanediol, and basic amino acid salts such as lysine and arginine.

The content of fatty acids contained in skin cleansers is not particularly limited. In the case of a cream-like skin cleanser, the content of fatty acid is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, and particularly preferably 30 to 50% by mass.

From the viewpoint of reducing the tightness of the skin cleanser after use, the content ratio of the water-soluble copolymer to the fatty acid is preferably 1:500~1:2, more preferably 1:200~1:3 , The best is 1:100~1:5.

In addition, from the viewpoint of improving the goodness of foamability, the content ratio of the water-soluble copolymer and the fatty acid is preferably 1:200~1:2, more preferably 1:100~1:5, especially It is preferably 1:50 to 1:10, and from the viewpoint of reducing the stickiness of the skin after use, the content ratio of the above-mentioned water-soluble copolymer to fatty acid is preferably 1:500 to 1:10. More preferably, it is 1:200~1:20, and especially good is 1:100~1:50.

(2-2) Skin cleanser containing nonionic surfactant

When the present invention is applied to a skin cleanser containing a nonionic surfactant, it can also more effectively reduce the tightness of the skin after use. As the nonionic surfactant, the above can be used without limitation.

In the form containing a nonionic surfactant, the content of the water-soluble copolymer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably from the viewpoint of reducing the tight feeling after use 1% by mass or more.

Also, from the viewpoint of improving the cleaning power, the content of the water-soluble copolymer is preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 3% by mass or more .

From the viewpoint of reducing the feeling of tightness after use of the skin cleanser, the content ratio of the water-soluble copolymer and the nonionic surfactant is preferably 1:20 to 1:0.5, and more preferably 1: 10~1: 0.7, especially good to become 1:5~1:1.

In addition, from the viewpoint of improving the cleaning power, the content ratio of the water-soluble copolymer and the nonionic surfactant is preferably 1:10~1:0.5, more preferably 1:5~1:0.5 , Better is 1:3~1:0.6, especially good is 1:1.5~1:0.7.

In addition, in the case of making a gel-like skin cleansing agent containing a nonionic surfactant, the water-soluble copolymer and the nonionic surfactant have The content ratio is preferably 1:15 to 1:0.7, more preferably 1:10 to 1:1, and particularly preferably 1:7 to 1:3.

[3] Other

The skin cleansing agent of the present invention may contain, in addition to the above-mentioned components, any components generally used in external skin preparations. As such arbitrary ingredients, particularly exemplified examples include Australian walnut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower seed oil, cottonseed oil, jojoba oil, coconut oil, palm oil , Liquid lanolin, hardened coconut oil, hardened oil, wood wax, hardened castor oil, beeswax, candelilla wax, carnauba wax, insect wax, lanolin, reduced lanolin, hard lanolin, jojoba wax, etc. Oils, waxes; flowing paraffin, squalane, iso Hydrocarbons such as octadecane, ceresin, paraffin, mineral wax, petrolatum, microcrystalline wax, etc.; oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, ten Higher fatty acids such as monoenoic acid; higher alcohols such as cetyl alcohol, stearyl alcohol, isostearyl alcohol, behenyl alcohol, octyldodecanol, myristyl alcohol, cetearyl alcohol, etc.; isooctanoic acid Cetyl ester, isopropyl myristate, cetyl isostearate, cetyl lactate, diisostearyl malate, ethylene glycol di-2-ethylhexanoate, neopentyl didecanoate Alcohol, glycerol di-2-heptyl undecanoate, glycerol tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triol Chains of synthetic ester oils such as isostearate, pentaerythritol tetra-2-ethylhexanoate, dimethyl polysiloxane, methylphenyl polysiloxane, diphenyl polysiloxane, etc. Polysiloxanes; cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecylcyclohexanesiloxane, etc.; amine-modified polysiloxane Alkanes, polyether modified polysiloxanes, alkyl modified polysiloxanes, fluorine modified polysiloxanes, modified polysiloxanes and other silicone oils; polyethylene glycol , Glycerin, 1,3-butanediol, erythritol, sorbitol, xylitol, maltitol, propylene glycol, dipropylene glycol, diglycerol, isopentanediol, 1,2-pentanediol Polyols such as alcohol, 2,4-hexanediol, 1,2-hexanediol, 1,2-octanediol, etc.; moisturizing components of sodium pyrrolidone carboxylate, lactic acid, sodium lactate, etc.; the surface can be classified Powders such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, silicic anhydride (silicon dioxide), aluminum oxide, barium sulfate, etc. that can be treated on the surface are iron red, yellow iron oxide, Inorganic pigments of black iron oxide, cobalt oxide, ultramarine, cyanine, titanium oxide, zinc oxide; pearlescent agents such as titanium mica, fish foil, bismuth oxychloride that can be treated on the surface; red color that can be laked No. 202, red 228 No., Red No. 226, Yellow No. 4, Blue No. 404, Yellow No. 5, Red No. 505, Red No. 230, Red No. 223, Orange No. 201, Red No. 213, Yellow No. 204, Yellow No. 203, Blue 1 Organic pigments such as No., green No. 201, purple No. 201, red No. 204, etc.; organic powders such as polymethyl methacrylate, nylon powder, organic polysiloxane elastomer, etc.; p-aminobenzoic acid series UV absorbers; o-aminobenzoic acid-based UV absorbers; salicylic acid-based UV absorbers, cinnamic acid-based UV absorbers, benzophenone-based UV absorbers; sugar-based UV absorbers, 2-(2'-hydroxyl) -5'-tert-butyloctylphenyl)benzotriazole, 4-methoxy-4'-tert-butyldibenzoylmethane and other ultraviolet absorbers; ethanol, isopropanol, etc. Lower alcohols; vitamin A or its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dioctanoate, vitamin B2 or its derivatives, vitamin B12, vitamin B15 or its derivatives, etc. Class B; Vitamin E of α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, etc., vitamin D, vitamin H, pantothenic acid, pantethine, pyrroloquinoline quinone, etc. Vitamins, etc.; antibacterial agents such as phenoxyethanol.

The skin cleansing agent of the present invention can be manufactured by processing the above-mentioned components according to a conventional method.

The invention is preferably applied to facial cleanser. According to the present invention, it is possible to provide a facial cleanser that does not easily make the skin feel tight after washing the face.

The sunscreen cosmetic of the present invention that solves the fifth problem is characterized by containing the above four components [1] to [4] as essential components. The components of [1] to [4] are detailed below.

<1> Component (A)... water-soluble copolymer [1] Hydrophobic monomer

The component (A) is a structural unit derived from the hydrophobic monomer represented by the general formula (1), (7) or (8) (hereinafter sometimes simply referred to as "constituent unit (7)", etc.) One or two or more water-soluble copolymers contained as essential constituent units.

Furthermore, in the present invention, "constituent unit derived from a monomer" refers to a constituent unit formed by cleaving a carbon-carbon unsaturated bond possessed by the corresponding monomer by a polymerization reaction.

Hereinafter, the hydrophobic monomer represented by the general formula (1), (7) or (8) will be described.

(1-1) Hydrophobic monomer represented by general formula (7)

In the aforementioned general formula (7), R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁵ represents a branched hydrocarbon group having 13 to 30 carbon atoms that does not contain a ring structure, or 2 that does not contain a ring structure. More than 6 branched hydrocarbon groups with 6 to 12 carbon atoms.

Here, examples of the alkyl group represented by R ¹⁴ include methyl, ethyl, propyl, isopropyl, and cyclopropyl. In the present invention, R ¹⁴ is preferably a hydrogen atom or a methyl group.

In addition, as a branched hydrocarbon group having a ring structure of 13 to 30 carbon atoms represented by R ¹⁵ , 1-methyldodecyl, 11-methyldodecyl, 3-ethylundecyl, 3 -Ethyl-4,5,6-trimethyloctyl, 1-methyltridecyl, 1-hexyloctyl, 2-butyldecyl, 2-hexyloctyl, 4-ethyl-1- Isobutyloctyl, 1-methylpentadecyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 16-methylheptadecyl, 9-methylheptadecyl, 7-methyl-2-(3-methylhexyl)decyl, 3,7,11,15-tetra-methylhexadecyl, 2-octyldodecyl, 2-decyltetradecyl, 2 -Twelve bases and sixteen bases.

In addition, examples of the hydrocarbon group having 6 or more carbon atoms and having 2 or more branches not containing a ring structure represented by R ¹⁵ include 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1-dimethylpentyl, 1-isopropylbutyl, 1-isopropyl-2-methylpropyl, 1,1-diethylpropyl, 1-ethyl-1-isopropylpropyl, 2-ethyl-4-methylpentyl, 1- Propyl-2,2-dimethylpropyl, 1,1,2-trimethyl-pentyl, 1-isopropyl-3-methylbutyl, 1,2-dimethyl-1-ethyl Butyl, 1,3-dimethyl-1-ethylbutyl, 1-ethyl-1-isopropyl-propyl, 1,1-dimethylhexyl, 1-methyl-1-ethyl Amylpentyl, 1-methyl-1-propylbutyl, 1,4-dimethylhexyl, 1-ethyl-3-methylpentyl, 1,5-dimethylhexyl, 1-ethyl -6-methylheptyl, 1,1,3,3-tetramethylbutyl, 1,2-dimethyl-1-isopropylpropyl, 3-methyl-1-(2,2- Dimethylethyl)butyl, 1-isopropylhexyl, 3,5,5-trimethylhexyl, 2-isopropyl-5-methylhexyl, 1,5-dimethyl-1-ethyl Hexyl, 3,7-dimethyloctyl, 2,4,5-trimethylheptyl, 2,4,6-trimethylheptyl, 3,5-dimethyl-1-(2, 2-dimethylethyl)hexyl and so on.

(1-2) Hydrophobic monomer represented by general formula (1) or (8)

In the aforementioned general formulas (1) and (8), R ¹ and R ¹⁶ represent a hydrogen atom or a C 1-3 alkyl group, and R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different , And represents a branched C 6-22 acyl group that does not contain a ring structure. X represents a group that desorbs the OH group from the triol.

Here, examples of the alkyl group represented by R ¹ and R ¹⁶ include methyl, ethyl, propyl, isopropyl, and cyclopropyl. In the present invention, R ¹ is preferably hydrogen or methyl.

In addition, examples of R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ^{19 that} do not contain a ring structure and have branched C 6-22 acyl groups include 2-methylpentyl acyl and 3-methyl Pentylpentyl, 4-methylpentyl, 2-ethylbutyryl, 2-ethylbutyryl, 2,2-dimethylbutyryl, 3,3-dimethylbutyryl, 2-methylhexyl , 4-methylhexyl, 5-methylhexyl, 2,2-dimethylpentyl, 4,4-dimethylpentyl, 2-methylheptyl, 2-ethyl Hexyl, 2-propylpentyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentyl, 2-methyloctyl, 3,3,5-trimethyl Hexamyl, 2-methylnonyl, 4-methylnonyl, 8-methylnonyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2- Tert-butylhexyl, 2,2-diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methyldecyl, 2-methyl-2-ethyloctyl, 2-methylundecyl, 10-methylundecyl, 2,2-dimethyldecyl, 2-ethyldecyl, 2- Butyloctyl, diethyloctyl, 2-third butyl-2,2,4-trimethylpentyl, 10-methyldodecyl, 3-methyldodecyl, 4-methyl Yldodecyl, 11-methyldodecyl, 10-ethylundecyl, 12-methyltridecyl, 2-butyldecyl, 2-hexyloctyl, 2-butyl -2-ethyloctyl, 12-methyltetradecyl, 14-methylpentadecyl, 2-butyldodecyl, 2-hexyldecyl, 16-methylheptadecyl, 2,2-Dimethylhexyl, 2-butylhexadecyl, 2-hexyldodecyl, 2,4,10,14-tetramethylpentyl, 18-methyl nineteen amide Base, 3,7,11,15-tetra-methylhexadecyl, 19-methyleicosyl, etc.

Moreover, in a preferred embodiment of the present invention, in the general formulas (1) and (8), R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ¹⁹ may be the same or different, and have no ring structure A branched carbon group with a carbon number of 10 to 22, or a ring group with no more than 2 branches and a carbon group with a carbon number of 6 to 9.

As such a preferred embodiment, R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ^{19 which} do not contain a ring structure and have a branched C 10-22 acyl group may include 2-methylnonyl Group, 4-methylnonylyl group, 8-methylnonylyl group, 4-ethyloctylyl group, 2-ethyloctylyl group, 2-butylhexylyl group, 2-butylhexylyl group, 2-third butylhexylyl group, 2, 2-Diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methyldecyl, 2-methyl-2-ethyloctyl , 2-methylundecyl, 10-methylundecyl, 2,2-dimethyldecyl, 2-ethyldecyl, 2-butyloctyl, diethyloctyl, 2 -Third-butyl-2,2,4-trimethylpentylyl, 10-methyldodecyl, 3-methyldodecyl, 4-methyldodecyl, 11-methyl Dodecanoyl, 10-ethylundecyl, 12-methyltridecyl, 2-butyldecyl, 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-methyl Yltetradecyl, 14-methylpentadecyl, 2-butyldodecyl, 2-hexyldecyl, 16-methylheptadecyl, 2,2-dimethylhexyl , 2-butylhexadecyl, 2-hexyldodecyl, 2,4,10,14-tetramethylpentyl, 18-methyl nonadecyl, 3,7,11,15- Tetramethyl hexadecyl, 19-methyl eicosyl, etc.

In addition, as a preferred embodiment, an acyl group having 6 to 9 carbon atoms having 2 or more branches and not containing a ring structure represented by R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ¹⁹ can be exemplified by 2 ,2-dimethylbutyryl, 3,3-dimethylbutyryl, 2,2-dimethylpentyl, 4,4-dimethylpentyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentanyl, 3,5,5-trimethylhexyl, etc.

In the general formula (1), the group derived from triol represented by X is not particularly limited as long as it is a group from which the OH group is desorbed from the triol. A group exemplified by a trihydric alcohol selected from the group consisting of glycerin, trimethylolpropane, and trimethylolethane desorbs the OH group is suitably exemplified.

In addition, in the general formula (8), the group derived from a tetrahydric alcohol represented by Y is not particularly limited as long as it desorbs the OH group from the tetrahydric alcohol, and can be appropriately exemplified by The tetrahydric alcohol of the group of alcohol, pentaerythritol, erythritol, D-threitol, and L-threitol desorbs the OH group.

In the present invention, it is particularly preferable to use a water-soluble copolymer containing the structural unit (1).

In a more preferred embodiment of the present invention, the hydrophobic monomer represented by the general formula (1) is the hydrophobic monomer represented by the general formula (15).

R ²⁴ and R ^{25 in the} general formula (15) are preferably branched carbon groups having 10 to 22 carbon atoms without a ring structure.

The carbon number of the acyl group of R ²⁴ and R ^{25 in} the general formula (15) is 12-22, more preferably 14-20, and particularly preferably 16-20.

In addition, the carbon number of the main chain of the acyl group of R ²⁴ and R ^{25 in} the general formula (15) is preferably 9 to 21, more preferably 12 to 20, and particularly preferably 16 to 18.

In addition, the branch number of the acyl group of R ²⁴ and R ^{25 in} the general formula (15) is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

In addition, in the acyl group of R ²⁴ and R ²⁵ in the general formula (15), the larger the position number of the carbon of the main chain of the branch chain bonding, the better. Specifically, the branched chain is preferably bonded to the first to third carbons at the end of the autonomous chain, more preferably the first or second carbon, and particularly preferably the first carbon.

As R ²⁴ and R ²⁵ , specifically, 10-methyl undecyl group, 10-methyl dodecyl group, 11-methyl dodecyl group, 10-ethyl undecyl group, 12-Methyltridecyl, 12-methyltetradecyl, 14-methylpentadecyl, 16-methylheptadecyl, 2,4,10,14-tetramethylpentyl , 18-methyl nineteen amide, 3,7,11,15-tetra-methyl hexadecyl, 19-methyl eicosyl, etc.

In the general formula (15), the group derived from triol represented by Z is not particularly limited as long as it desorbs the OH group from the triol, and can be appropriately exemplified by a group selected from the group consisting of glycerol and triol. The trihydric alcohol of the group of methylolpropane and trimethylolethane desorbs the OH group.

[2] Hydrophilic monomer

As the hydrophilic monomer of the water-soluble copolymer constituting the component (A), a polymerizable carboxylic acid and compounds represented by the general formula (2), the general formulas (9), (10), and (11) can be used .

(2-1) polymerizable carboxylic acid,

In the present invention, specific examples of the polymerizable carboxylic acid or its salt include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid and its sodium, potassium, ammonium, and amine salts. . Among these, acrylic acid, methacrylic acid, and their salts are particularly preferred from the viewpoint of high polymerizability. When the water-soluble copolymer of the present invention is introduced into a structural unit derived from a polymerizable carboxylate, the polymerizable carboxylic acid may be prepared as a salt in advance to perform a polymerization reaction, or the polymerization reaction may be used to derive the self-polymerizable carboxylic acid After the constituent units are derived into water-soluble copolymers, they are made into salts by neutralization with alkali.

(2-2) Hydrophilic monomer represented by general formula (2)

In the aforementioned general formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁶ represents a hydrogen atom and a carbon atom having 6 to 6 carbon atoms The aromatic hydrocarbon group of 10, the aliphatic hydrocarbon group of 1 to 14 carbon atoms, or the acyl group of 1 to 12 carbon atoms. n represents an integer of 6~40.

Examples of the alkyl group represented by R ⁴ in the general formula (2) include methyl, ethyl, propyl, isopropyl, and cyclopropyl. In the present invention, R ⁴ is preferably a hydrogen atom or a methyl group.

In addition, as the alkylene group represented by R ⁵ , ethyl group, ethyl group, isopropyl group, 2-hydroxypropyl group, 2-hydroxy-2-methyl ethyl group, 2-hydroxy- 1-methylethylidene, etc. Among these, ethylidene or propylidene are preferred, and ethylidene is more preferred.

In addition, among the groups represented by R ⁶ , examples of the aromatic groups having 6 to 10 carbon atoms include phenyl, benzyl, tolyl, and ethylphenyl groups. As the aliphatic hydrocarbon groups having 1 to 14 carbon atoms, Appropriate examples include methyl, ethyl, butyl, tertiary butyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, lauryl, etc.; as a C 1-12 acyl group, a methyl acyl group can be appropriately exemplified. , Acetyl, propyl, butyl, isobutyl, pentyl, lauryl, etc. Among these, the group represented by R ^{5 is} preferably an aliphatic hydrocarbon group having 1 to 14 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.

Furthermore, n in the general formula (2) is in the range of 6 to 40.

Among the monomers represented by the general formula (2), as the monomer in which R ⁵ is propylene, specifically, polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, poly Propylene glycol (9) monomethacrylate, polypropylene glycol (13) monomethacrylate, etc. Furthermore, the number in parentheses indicates N. Most of these polymers are available as commercial products. Specific examples of these commercially available products include trade names "Blenmer" AP-400, AP-550, AP-800, PP-500, and PP-800 (all manufactured by Nippon Oil & Fats Co., Ltd.).

Among the monomers represented by the general formula (2), as the monomer in which R ⁵ is an ethylidene group, specifically, polyethylene glycol (10) monoacrylate, polyethylene glycol (8) monomer Methacrylate, polyethylene glycol (23) monoacrylate, polyethylene glycol (23) monomethacrylate, methoxypolyethylene glycol (9) acrylate, methoxypolyethylene glycol ( 9) Methacrylate, methoxypolyethylene glycol (23) methacrylate, oleyloxy polyethylene glycol (18) methacrylate, lauryloxy polyethylene glycol (18) acrylate, Lauryloxy polyethylene glycol (10) methacrylate, stearyl polyethylene glycol (30) monomethacrylate, etc.

The above-mentioned hydrophilic monomers can be obtained in a high yield by esterification reaction of corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride. In addition, since many commercial products already exist, the commercial products can also be used. As such a commercially available product, specifically, the trade names of Blenmer, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, and PSE-1300 (all of which are Japanese oil ) System) etc.

(2-3) Hydrophilic monomer represented by general formula (9)

As the hydrophilic monomer of the present invention, the hydrophilic monomer represented by the above general formula (9) can also be used.

Specific examples of the hydrophilic monomer represented by the general formula (9) include 2-acryloyloxyethyl phosphate choline (APC) and 2-methacryloyloxyethyl phosphate choline ( MPC). Such monomers can be synthesized by the following method described in Polymer Journal, Vol22, No. 5, for example.

<synthesis method>

Reacting 2-bromoethylphosphoryl dichloride with 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate to obtain 2-methacryloxyethyl-2'-bromoethyl phosphoric acid or 2- After acryloyloxyethyl-2'-bromoethyl phosphoric acid, these compounds are reacted with triethylamine in methanol.

(2-4) Hydrophilic monomer represented by general formula (10)

As the hydrophilic monomer of the present invention, the hydrophilic monomer represented by the above general formula (10) can also be used.

Among the hydrophilic monomers represented by the general formula (10), the reducing sugar that is a group that removes hydrogen from the hydroxyl group at the 1-position of the reducing sugar represented by GO- can be specifically selected from the group consisting of glucose and mannose. Groups of monosaccharides such as sugar, galactose, arabinose, xylose, ribose, disaccharides such as maltose, lactose, cellobiose, trisaccharides such as maltotriose, and oligosaccharides such as maltooligosaccharide One or two or more, among which one or two or more selected from the group consisting of glucose, galactose, arabinose, xylose, ribose, maltose, lactose, and cellobiose is preferred, and glucose is particularly preferred. Further, as the monomer represented by the general formula (10), glucosyloxyethyl methacrylate (hereinafter abbreviated as GEMA) or glucosyloxyethyl acrylate (hereinafter abbreviated as GEA) is preferred.

(2-5) Hydrophilic monomer represented by general formula (11)

As the hydrophilic monomer of the present invention, the hydrophilic monomer represented by the above general formula (11) can also be used.

In the monomer of the general formula (11), the amino acid as the amino acid residue represented by R ²³ is not particularly limited as long as it is a generally known amino acid, and specifically, glycine can be exemplified. Acid, alanine, glutamic acid, lysine, spermine, etc. Among these, since the skin barrier effect of the water-soluble copolymer obtained is good, ionic acid residues are particularly preferable.

In addition, the polyamine of the polyamine residue represented by R ²³ means an amine having two or more amine groups that can be substituted with an alkyl group in the same molecule. Specifically, a diamine, triamine, tetraamine or An amine in which the hydrogen atom of the amine group is substituted with an alkyl group. Among these, from the viewpoint of excellent use of skin external preparations containing the obtained water-soluble copolymer, diamine is preferable, and as a particularly preferable specific example, from the viewpoint of ease of obtaining raw materials at the time of synthesis, Examples include ethylenediamine, 1,4-diamino-n-butane, 1,6-diamino-n-hexane, and the like.

The amine alcohol as the amine alcohol residue represented by R ²³ means a compound having an alkyl-substituted amine group and an alcoholic hydroxyl group in the same molecule. The amino alcohol is not particularly limited as long as it is generally known, and specific examples include ethanolamine, triethylaminoethanol, and the like.

The salt of the monomer represented by the general formula (11) is not particularly limited, and specifically, there can be exemplified sodium salts, potassium salts, ammonium salts, amine salts and the like neutralized with an acid moiety, or Partially acid neutralized hydrochloride, sulfate, nitrate, phosphate, citrate, oxalate, carbonate, etc. When the water-soluble copolymer of the present invention is introduced into the structural unit derived from the monomer salt represented by the general formula (11), the monomer represented by the general formula (11) may be prepared as a salt in advance to perform a polymerization reaction, or Using a polymerization reaction, the structural unit derived from the monomer represented by the general formula (11) is derived as a water-soluble copolymer, and then neutralized to form a salt.

As a specific example of the salt of the monomer represented by the general formula (11), compounds 1 to 11 and salts thereof can be appropriately exemplified.

The hydrophilic monomer represented by the general formula (11), for example, as shown in the aforementioned reaction formulas (1) and (2), can be obtained by an esterification reaction using (meth)acrylic acid or (meth)acryloyl chloride , Amidation reaction synthesis.

As described above, in the present invention, as the hydrophilic polymer, the aforementioned general formulas (2), (9), (10), and (11) can be used.

In a preferred embodiment of the present invention, the water-soluble copolymer contains the structural unit (2) derived from the aforementioned general formula (2).

[3] Water-soluble copolymer

In the present invention, a water-soluble copolymer having a structural unit (1) and a structural unit (2) is particularly applicable. Furthermore, it is more preferable to use a water-soluble copolymer having a structural unit (15) and a structural unit (2).

Among such water-soluble copolymers, (methoxy methacrylate PEG-23/diisostearic acid glyceryl methacrylate) copolymer can be particularly preferably used.

By containing such a water-soluble copolymer, it can be an emulsified composition with low irritation, less stickiness, and excellent emulsification stability.

(Methoxy methacrylate PEG-23/diisostearic acid glyceryl methacrylate) copolymer, as the constituent unit (g), mainly contained in the hydrophobic monomer represented by the general formula (15), R ²⁴ and R ²⁵ are structural units (g) derived from a hydrophobic monomer of 16-methylheptadecyl group.

Moreover, as a structural unit (h), it is mainly comprised from the hydrophilic monomer represented by the said general formula (2), R ⁴ is a methyl group, R ⁵ is an ethyl group, R ⁶ is a methyl group, and n is 23 The constituent unit (h) derived from a hydrophilic monomer.

In the present invention, the proportion of the structural units (g) of the water-soluble copolymer in all the structural units is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and 10 to 30% by mass.

By setting the proportion of the constitutional unit (g) of the water-soluble copolymer within the aforementioned range, it is possible to provide sunscreen cosmetics having a good moisturizing feeling and further reducing the stickiness.

In the present invention, the proportion of the constituent units (h) of the water-soluble copolymer in all constituent units is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and 70 to 90% by mass.

By making the proportion of the structural unit (h) of the water-soluble copolymer within the aforementioned range, it is possible to provide sunscreen cosmetics with good moisturizing feeling and further reducing stickiness.

In the present invention, the mass ratio of the structural unit (g) and the structural unit (h) constituting the water-soluble copolymer is preferably 5:95 to 50:50, further preferably 10:90 to 45:55, and more The best is 20:80~40:60, and the best is 25:75~35:65.

Moreover, the molar ratio of the structural unit (g) and the structural unit (h) constituting the water-soluble copolymer is preferably 8:92 to 62:38, further preferably 15:85 to 57:43, and more preferably 29:71~52:48, especially good is 35:65~46:54.

By setting the mass ratio and the molar ratio of the constitutional unit (g) and constitutional unit (h) of the water-soluble copolymer to the aforementioned range, the sense of use of the sunscreen cosmetics can be further improved.

In the present invention, the average molecular weight of the water-soluble copolymer is preferably from 20,000 to 110,000, further preferably from 20,000 to 80,000, more preferably from 30,000 to 80,000, even more preferably from 40,000 to 70,000, and particularly preferably from 50,000 to 70,000. Further particularly preferred is 57000~66000.

The content of the water-soluble copolymer is not particularly limited, but it is usually 0.001 to 15% by mass, preferably 0.01 to 10% by mass.

<2> Ingredient (B)... polyglycerol fatty acid ester

The sunscreen cosmetic of the present invention is characterized by comprising as a component (B) a polyglycerol fatty acid ester formed by condensing 1 molecule of polyglycerol with a polymerization degree of 10 and 2 to 5 molecules of fatty acid esters having a carbon number of 16 or more.

The polyglycerin fatty acid ester constituting the component (B) may have a branched chain fatty acid having a carbon number of 16 or more, and may be saturated or unsaturated.

Especially exemplified oleic acid and isostearic acid.

In addition, the number of molecules of fatty acid ester-bonded to 1 molecule of polyglycerin may be 2 to 5, preferably 5 molecules.

In the present invention, polyglycerol pentastearate-10 can be particularly used as component (B).

The content of the polyglycerin fatty acid ester of the component (B) can be generally 0.1 to 10% by mass.

From the viewpoint of improving the stability of emulsification, the content of component (B) is 0.3% by mass or more, more preferably 0.5% by mass, and particularly preferably 0.7% by mass or more.

Furthermore, from the viewpoint of suppression of stickiness, the content of component (B) is preferably 7 mass% or less, more preferably 5 mass% or less, and particularly preferably 3 mass% or less.

<3> Component (C)...ionic surfactant

The sunscreen cosmetic of the present invention contains an ionic surfactant as component (C). As an ionic surfactant, as long as For cosmetics, it is not particularly limited, and any of anionic surfactants, cationic surfactants, and amphoteric surfactants can be used.

As anionic surfactants, specific examples include fatty acid soaps such as sodium fatty acid, potassium fatty acid, and fatty acid triethanolamine, sodium lauryl sulfate, potassium lauryl sulfate, and triethanolamine lauryl sulfate, which may have polyoxyethylene groups. Alkyl sulfate which may have polyoxyethylene alkyl sulfate salt, acyl lactylate, sodium lauryl phosphate which may have polyoxyethylene, potassium lauryl phosphate, triethanolamine lauryl phosphate, etc. Phosphate salt, alkyl sulfosuccinate, etc.

As cationic surfactants, particularly exemplified examples are alkyl trimethyl ammonium salt, alkyl pyridine salt, distearyl dimethyl ammonium chloride dialkyl dimethyl ammonium salt, chlorinated poly(N, N'-dimethyl-3,5-methylenepiperidine), alkyl quaternary ammonium salt, alkyl dimethyl benzyl ammonium salt, alkyl isoquinoline salt, dialkyl morpholine salt, POE-alkylamine, alkylamine salt, polyamine fatty acid derivative, pentanol fatty acid derivative, xylylenediamine chloride, benzethonium chloride, etc.

Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants and betaine-based surfactants.

Among the above-mentioned surfactants, as the component (C), it is preferable to use an anionic surfactant, and it is preferable to use an acyl lactate.

As the sodium lactate, sodium salt is preferred, and specifically, sodium lauryl lactate, isostearyl sodium lactate, sodium stearyl lactylate and the like are particularly exemplified.

The content of the ionic surfactant is not particularly limited, but it is usually 0.01 to 2.0% by mass, more preferably 0.1 to 1% by mass.

From the viewpoint of improving the stability of emulsification, the content of the ionic surfactant is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, and particularly preferably 0.1% by mass or more.

Furthermore, from the viewpoint of suppression of stickiness, the content of the ionic surfactant is preferably 1.5% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

<4> Component (D)... UV scattering agent and/or UV absorbent

The sunscreen cosmetic of the present invention contains an ultraviolet scattering agent and/or an ultraviolet absorbent as component (D).

The ultraviolet scattering agent refers to a fine-grained metal oxide that has an effect of scattering ultraviolet rays, and as long as it can be blended into an emulsified cosmetic, its type is not particularly limited. Examples of metal oxides include titanium dioxide, zinc oxide, zirconium oxide, and cerium oxide.

The content of the ultraviolet scattering agent is not particularly limited, but it is usually 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and particularly preferably 1 to 10% by mass.

The ultraviolet scattering agent has a particle diameter called fine particles in the technical field. For example, the first-order particle size observed with an electron microscope is usually 5 nm or more, preferably 10 nm or more, and usually 100 nm or less, preferably 80 nm The following.

It is preferable that the ultraviolet scattering agent used in the present invention contains at least one selected from the group consisting of particulate titanium dioxide and particulate zinc oxide from the viewpoint of excellent ultraviolet scattering effect.

The ultraviolet scattering agent used in the present invention can be prepared by a common method such as thermal decomposition of the metal salt in the gas phase, but since there are many commercial products, commercial products can also be used directly. As such a commercially available product, specifically, as fine particle titanium dioxide, "MTY-110M3S" (made by Tayca), "MTY-02" (made by Tayca), and "MT-100TV" (Tayca) (Share system), ``MT-500HSA'' (Tayca (share) system), ``MT-100T'' (Tayca (share) system), ``MT-01'' (Tayca (share) system), ``MT-10EX'' (Tayca (share) system), ``MT-05'' (Tayca (share) system), ``MT-100Z'' (Tayca (share) system), ``MT-150EX'' (Tayca (share) system), ``MT- 100AQ'' (Tayca (share) system), ``MT-100WP'' (Tayca (share) system), ``MT-100SA'' (Tayca (share) system), ``MT-500B'' (Tayca (share) system), `` MT-500SA (Tayca (share) system), MT-600B (Tayca (share) system), MT-500SAS (Tayca (share) system), TIPAQUE CR-50 (Ishihara Industries (share) System), ``TIPAQUE TTO-M-1'' (Ishihara Industry Co., Ltd. system), ``TIPAQUE TTO-V4'' (Ishihara Industry Co., Ltd. system), ``ST-455'' (Titan Kogyo Co., Ltd. system), `` "STT-65C-S" (Titan Kogyo Co., Ltd.), "STT-30EHS" (Titan Kogyo Co., Ltd.), "Bayer Titan R-KB-1" (Bayer Co., Ltd.), etc.

In addition, as fine particulate zinc oxide, "MZ-300" (made by Tayca Corporation), "MZY-303S" (made by Tayca Corporation), "MZ-306X" (made by Tayca Corporation), and " MZ-500'' (Tayca (share) system), ``MZY-505S'' (Tayca (share) system), ``MZ-506X'' (Tayca (share) system), ``MZ-510HPSX'' (Tayca (share) system) , "WSX-MZ-700" (Tayca (share) system), "SAMT-UFZO-450" (Miyoshi Chemical (share) system), "SAMT-UFZO-500" (Miyoshi Chemical (share) system), "FZO -50" (Stone The original industry (share system), "Maxlight ZS-032" (Showa Denko (share) system), "Maxlight ZS-032" (Showa Denko (share) system), etc.

In the present invention, the ultraviolet scattering agent is preferably coated with an inorganic compound such as silica or alumina, or an organic compound such as sodium polyacrylate, fatty acid metal soap, or silicone.

The ultraviolet scattering agent has better water dispersibility. Because the water-dispersible ultraviolet scattering agent is uniformly dispersed in the water phase, the sunscreen cosmetic of the present invention in such a form has a good ultraviolet defense function.

As the water-dispersible ultraviolet scattering agent, an ultraviolet scattering agent whose surface is coated with a hydrophilic compound is particularly exemplified.

As such a water-dispersible ultraviolet scattering agent, an ultraviolet scattering agent surface-treated with sodium polyacrylate is preferred. The sunscreen cosmetic of the present invention containing the ultraviolet scattering agent surface-treated with sodium polyacrylate as the component (D) has excellent dispersibility and excellent ultraviolet defense function.

The ultraviolet absorber is not particularly limited as long as it can be blended into general emulsified cosmetics, but in order to absorb ultraviolet light of a wide wavelength, it includes UV-A that absorbs ultraviolet light of a wavelength of 320 to 400 nm (A region) An absorber and a UV-B absorber that absorbs ultraviolet rays with a wavelength of 290 to 320 nm (B region) are preferred.

The content of the ultraviolet absorber is not particularly limited, but it is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, and usually 20% by mass or less, preferably 15% by mass or less, More preferably, it is 10 mass% or less.

、亞甲基雙苯并三唑基四甲基丁酚、二乙基胺基羥基苯甲醯基苯甲酸己酯、第三丁基甲氧基二苯甲醯基甲烷等之化合物。其中，從紫外線吸收能佳之觀點，尤以二乙基胺基羥基苯甲醯基苯甲酸己酯、及第三丁基甲氧基二苯甲醯基甲烷特佳。因為該等之化合物中存在有市售品，所以可直接使用市售品。作為具體的市售品，可例示「Uvinul A Plus Granular」(二乙胺基羥基苯甲醯基苯甲酸己酯BASF公司製)、「Parsol 1789」(第三丁基甲氧基苯甲醯基甲烷DSM公司製)。 As a UV-A absorber, 2-hydroxy-4-methoxybenzophenone, 2-(2'-hydroxy-5'-tolyl)benzotriazole, dimethoxybenzylidene can be exemplified 2-ethylhexyl imidazolidinepropionate, bis (retinoic acid)

, Methylene bis benzotriazolyl tetramethyl butanol, diethylamino hydroxybenzoyl benzoic acid hexyl ester, the third butyl methoxy dibenzoyl methane compound. Among them, from the viewpoint of excellent ultraviolet absorption, hexyl diethylaminohydroxybenzoyl benzoate and tert-butyl methoxydibenzoyl methane are particularly preferred. Since there are commercial products in these compounds, commercial products can be used directly. As specific commercial products, "Uvinul A Plus Granular" (diethylaminohydroxybenzoyl benzoyl hexyl ester manufactured by BASF Corporation), "Parsol 1789" (third butyl methoxy benzoyl carbamoyl methane DSM) can be exemplified Company system).

The content of the UV-A absorbent is usually 0.01% by mass or more, preferably 0.1% by mass or more, and usually 5% by mass or less, preferably 3% by mass or less.

、2-羥基-4-甲氧基二苯甲酮、水楊酸高薄荷酯、水楊酸辛酯等之化合物。因為該等之化合物中存在有市售品，所以可直接使用市售品。作為具體的市售品，可例示「Uvinul MC80」(對甲氧基肉桂酸2-乙基己酯BASF公司製)、「Uvinul T150」(2,4,6-三苯胺基-p-(碳-2’-乙基己基-1’-氧基)-1,3,5-三

BASF公司製)、「Uvinul M40」(2-羥基-4-甲氧基二苯甲酮BASF公司製)、「Parsol SLX」(二甲聚矽氧烷二乙基苯亞甲基丙二酸酯DSM公 司製)、「Parsol 340」(2-氰基-3,3-二苯基丙烯酸2-乙基己酯DSM公司製)、「Parsol HMS」(水楊酸高薄荷酯DSM公司製)、「Parsol HMS」(水楊酸辛酯DSM公司製)。 Specific examples of the UV-B absorber include 2-ethylhexyl p-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and dimethyl poly Siloxane diethylbenzylidene malonate, 2,4,6-triphenylamino-p-(carbon-2'-ethylhexyl-1'-oxy)-1,3,5- three

, 2-hydroxy-4-methoxybenzophenone, high menthyl salicylate, octyl salicylate and other compounds. Since there are commercial products in these compounds, commercial products can be used directly. As specific commercially available products, "Uvinul MC80" (p-methoxycinnamic acid 2-ethylhexyl ester manufactured by BASF Corporation) and "Uvinul T150" (2,4,6-triphenylamino-p-(carbon -2'-ethylhexyl-1'-oxy)-1,3,5-tri

(Made by BASF), "Uvinul M40" (2-hydroxy-4-methoxybenzophenone made by BASF), "Parsol SLX" (dimethicone diethylbenzylidene malonate DSM), "Parsol 340" (2-cyano-3,3-diphenylacrylic acid 2-ethylhexyl DSM), "Parsol HMS" (high menthyl salicylate DSM), "Parsol HMS" (manufactured by DSM Corporation).

The content of the UV-B absorbent is usually 0.1% by mass or more, preferably 0.5% by mass or more, and usually 10% by mass or less, preferably 7% by mass or less.

<5> Other components

The components contained in the oil phase and the water phase are not particularly limited.

Examples of the oil agent constituting the oil phase include liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, and silicone oils.

Examples of the liquid fats and oils include avocado oil, camellia oil, turtle oil, Australian walnut oil, corn oil, mink oil, olive oil, rapeseed oil, egg butter, sesame oil, apricot kernel oil, wheat germ oil, and camellia Oil, castor oil, linseed oil, safflower seed oil, cottonseed oil, perilla oil, white awn flower seed oil, soybean oil, peanut oil, bitter tea oil, Japanese cypress seed oil, rice bran oil, bougainvillea oil, Japanese tung oil, Dutch Jojoba oil, germ oil, triglycerin, trioctanoic acid glycerin, triisopalmitic acid glycerin, etc.

Examples of solid oils and fats include cocoa butter, coconut oil, horse fat, hardened coconut oil, palm oil, tallow, sheep fat, hardened tallow, palm kernel oil, lard, beef bone fat, wood wax kernel oil, hardened oil, Shea butter, wood wax, hardened castor oil, etc.

Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, insect wax, spermaceti wax, montan wax, bran wax, lanolin, kapok wax, lanolin acetate, and liquid Lanolin, sugar cane wax, Lanolin fatty acid isopropyl ester, hexyl laurate, reduced lanolin, jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid Polyethylene glycol, POE hydrogenated lanolin alcohol ether, etc.

Examples of the hydrocarbon oil include fluid paraffin, ozokerite, isooctadecane, paraffin, mineral wax, squalene, petrolatum, and microcrystalline wax.

Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid (behenic acid), 12-hydroxystearic acid, undecylenic acid, and tall oil. .

Examples of higher alcohols include cetyl alcohol, stearyl alcohol, behenyl alcohol, squalanol, myristyl alcohol, and cetearyl alcohol.

Examples of synthetic ester oils include isopropyl myristate, cetyl caprylate, octyl dodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, and myristate myristate. Ester, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, sucrose hard Fatty acid ester, sucrose oleate, cholesterol 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkanediol monoisostearate, didecane Neopentyl glycol acid, diisostearyl malate, glycerol di-2-heptyl undecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triiso Stearate, pentaerythritol tetra-2-ethylhexanoate, glycerol tri-2-ethylhexanoate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate , 2-ethylhexyl palmitate, glycerol trimyristate, tri-2-heptyl undecyl glyceride, castor oil fatty acid methyl ester, oleic oleate, cetearyl alcohol, glycerol acetate Ester, palmitic acid 2- Heptyl undecyl ester, cetyl palmitate, diisobutyl adipate, N-lauryl-L-glutamic acid-2-octyl dodecyl ester, di-2-heptyl adipate Monoester, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, disebacate Isopropyl ester, 2-ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, etc.

Examples of the silicone oil include chain polysiloxanes such as dimethyl polysiloxane, methyl phenyl polysiloxane, methyl hydrogen polysiloxane, and decamethyl polysiloxane. Cyclic polysiloxane such as dodecyl polysiloxane, tetramethyl tetrahydropolysiloxane, etc.

One oil or two or more oils can be used.

The sunscreen cosmetics of the present invention may be blended with any additional ingredients usually blended in cosmetics, as long as the effects of the present invention are not impaired. As such added components, for example, moisturizing agents such as polyethylene glycol, glycerin, 1,3-butanediol, erythritol, sorbitol, xylitol, and maltitol; ethanol, etc. Lower alcohols; antioxidants such as butylhydroxytoluene, tocopherol, phytic acid, etc.; antibacterial agents such as benzoic acid, salicylic acid, sorbic acid, alkyl p-hydroxybenzoate, hexachlorophenol, etc.; acetyl sarcosinate (eg , Sodium lauryl sarcosinate), glutathione, citric acid, malic acid, tartaric acid, lactic acid and other organic acids; vitamin A and its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 Dicaprylate, Vitamin B2 and its derivatives, Vitamin B12, Vitamin B15 and its derivatives, Vitamin B, α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, etc. Vitamin E, Vitamin D, Vitamin H, pantothenic acid, pantethine, niacinamide, nicotinic acid benzyl Vitamins such as esters; γ-glycosan, allantoin, glycyrrhizic acid (salt), glycyrrhetinic acid and its derivatives, tranexamic acid and its derivatives [as tranexamic acid derivatives, tranexamic acid two Polymers (for example, trans-4-hydrochloric acid (trans-aminomethylcyclohexanecarbonyl) aminemethylcyclohexanecarboxylic acid, etc.), esters of tranexamic acid and hydroquinone (for example, trans-4- Aminomethylcyclohexanecarboxylic acid 4'-hydroxyphenyl ester, etc.), esters of tranexamic acid and gentisic acid (for example, 2-(trans-4-aminomethylcyclohexylcarbonyloxy)-5-hydroxyl Benzoic acid and its salts, etc., tranexamic acid amide (for example, trans-4-amine methylcyclohexanecarboxylic acid methyl amide and its salt, trans-4-(P-methoxybenzene (Formyl) amine methylcyclohexane carboxylic acid and its salt, trans-4-guanidine methylcyclohexane carboxylic acid and its salt, etc.]), cypressol, myrrhol, cineol, thyme Saponins such as phenol, inositol, Bupleurum saponin, ginseng saponin, luffa saponin, saponin saponin, pantothenyl alcohol diethyl ether, ethinyl estradiol, tranexamic acid, arbutin, ceresin, placenta, etc. Various medicaments; Bauhinia, Sophora flavescens, Japanese wing grass, orange, sage, yarrow, mallow, Chinese medicine, thyme, angelica, spruce, birch, quince, loofah, horse chestnut, tiger ear Extracts of plants such as grass, rabbit chrysanthemum, lily, sagebrush, peony, aloe, gardenia, Japanese cypress, etc.; pigments; porous and/or water-absorbing powders (for example, starches obtained from corn or potatoes, etc.) , Silicic anhydride, talc, kaolin, aluminum magnesium silicate, calcium alginate, etc.); neutralizing agent; preservative; fragrance; pigment, etc.

The sunscreen cosmetic of the present invention can be produced by the following method, for example.

The oil agent and the component (B) are mixed, and then the other oil phase components are mixed and dissolved by heating to prepare a mixture of oil phase components. When an ultraviolet scattering agent (component (D)) is included, an ultraviolet scattering agent is added to the mixture and dispersed using a disperser.

Next, the water phase component and the component (C) are mixed, the mixture of the oil phase component is added during heating, and emulsified with a homogenizer. After emulsification, the sunscreen cosmetic of the present invention can be produced by adding component (A) and optionally adding a water-dispersible ultraviolet scattering agent (component (D)) and cooling while stirring and mixing.

<1> Coating with sea island structure

The island-in-sea structure refers to a structure in which two types of polymers that are incompatible with each other cause phase separation, and a continuous phase containing one polymer is dispersed with a dispersed phase containing the other polymer. Then, the continuous phase of the sea island structure is called the sea phase, the dispersed phase is called the island phase, and the particles of the dispersed phase are called island particles.

The film of the present invention has an island-in-sea structure in which island particles containing an amphiphilic copolymer are dispersed in a marine phase containing an aqueous gel formed of a water-soluble polymer.

Then, the amphiphilic copolymer contained in the island particles has a structural unit (i) and a structural unit (j) as necessary structural units.

The structural unit (i) is one or more structural units derived from a hydrophobic monomer, and the structural unit (j) is one or more structural units derived from a hydrophilic monomer.

The film of the present invention having such a structural feature, regardless of whether or not the aqueous component is the main component, has a touch like milk containing oil.

The coating of the present invention will be described in further detail below.

<1-1> Island particles

In the present invention, the amphiphilic copolymer contained in the island-in-the-sea island particles has a structural unit derived from the aforementioned hydrophobic monomer The element (i) and the structural unit (j) derived from the aforementioned hydrophilic monomer are necessary structural units.

As the amphiphilic copolymer of the present invention, a water-soluble copolymer containing a structural unit derived from the hydrophobic monomer and the hydrophilic monomer described in [1] and [2] below is preferably used.

[1] Hydrophobic monomer

In the present invention, a structural unit derived from the hydrophobic monomer represented by the general formula (1), (7) or (8) (hereinafter sometimes simply referred to as "constituent unit (7)" etc.) is used One kind or two or more kinds of amphiphilic copolymers (also referred to as acrylic amphiphilic copolymers) which are necessary constituent units are preferable.

Furthermore, in the present invention, "constituent unit derived from a monomer" refers to a constituent unit formed by cleaving a carbon-carbon unsaturated bond possessed by the corresponding monomer by a polymerization reaction.

Hereinafter, the hydrophobic monomer represented by the general formula (1), (7) or (8) will be described.

(1-1) Hydrophobic monomer represented by general formula (7)

In the aforementioned general formula (7), R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹⁵ represents a branched hydrocarbon group having 13 to 30 carbon atoms that does not contain a ring structure, or 2 that does not contain a ring structure. More than 6 branched hydrocarbon groups with 6 to 12 carbon atoms.

Here, examples of the alkyl group represented by R ¹⁴ include methyl, ethyl, propyl, isopropyl, and cyclopropyl. In the present invention, R ¹⁴ is preferably a hydrogen atom or a methyl group.

In addition, as a branched hydrocarbon group having a ring structure of 13 to 30 carbon atoms represented by R ¹⁵ , 1-methyldodecyl, 11-methyldodecyl, 3-ethylundecyl, 3 -Ethyl-4,5,6-trimethyloctyl, 1-methyltridecyl, 1-hexyloctyl, 2-butyldecyl, 2-hexyloctyl, 4-ethyl-1- Isobutyloctyl, 1-methylpentadecyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldodecyl, 16-methylheptadecyl, 9-methylheptadecyl, 7-methyl-2-(3-methylhexyl)decyl, 3,7,11,15-tetra-methylhexadecyl, 2-octyldodecyl, 2-decyltetradecyl, 2 -Twelve bases and sixteen bases.

In addition, examples of the hydrocarbon group having 6 or more carbon atoms and having 2 or more branches not containing a ring structure represented by R ¹⁵ include 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1,1-dimethylpentyl, 1-isopropylbutyl, 1-isopropyl-2-methylpropyl, 1,1-diethylpropyl, 1-ethyl-1-isopropylpropyl, 2-ethyl-4-methylpentyl, 1- Propyl-2,2-dimethylpropyl, 1,1,2-trimethyl-pentyl, 1-isopropyl-3-methylbutyl, 1,2-dimethyl-1-ethyl Butyl, 1,3-dimethyl-1-ethylbutyl, 1-ethyl-1-isopropyl-propyl, 1,1-dimethylhexyl, 1-methyl-1-ethyl Amylpentyl, 1-methyl-1-propylbutyl, 1,4-dimethylhexyl, 1-ethyl-3-methylpentyl, 1,5-dimethylhexyl, 1-ethyl -6-methylheptyl, 1,1,3,3-tetramethylbutyl, 1,2-dimethyl-1-isopropylpropyl, 3-methyl-1-(2,2- Dimethylethyl)butyl, 1-isopropylhexyl, 3,5,5-trimethylhexyl, 2-isopropyl-5-methylhexyl, 1,5-dimethyl-1-ethyl Hexyl, 3,7-dimethyloctyl, 2,4,5-trimethylheptyl, 2,4,6-trimethylheptyl, 3,5-dimethyl-1-(2, 2-dimethylethyl)hexyl and so on.

(1-2) Hydrophobic monomer represented by general formula (1) or (8)

In the aforementioned general formulas (1) and (8), R ¹ and R ¹⁶ represent a hydrogen atom or a C 1-3 alkyl group, and R ² , R ³ , R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different , And represents a branched C 6-22 acyl group that does not contain a ring structure. X represents a group that desorbs the OH group from the triol.

Here, examples of the alkyl group represented by R ¹ and R ¹⁶ include methyl, ethyl, propyl, isopropyl, and cyclopropyl. In the present invention, R ³ is preferably a hydrogen atom or a methyl group.

In addition, examples of R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ^{19 that} do not contain a ring structure and have branched C 6-22 acyl groups include 2-methylpentyl acyl and 3-methyl Pentylpentyl, 4-methylpentyl, 2-ethylbutyryl, 2-ethylbutyryl, 2,2-dimethylbutyryl, 3,3-dimethylbutyryl, 2-methylhexyl , 4-methylhexyl, 5-methylhexyl, 2,2-dimethylpentyl, 4,4-dimethylpentyl, 2-methylheptyl, 2-ethyl Hexyl, 2-propylpentyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentyl, 2-methyloctyl, 3,3,5-trimethyl Hexamyl, 2-methylnonyl, 4-methylnonyl, 8-methylnonyl, 4-ethyloctyl, 2-ethyloctyl, 2-butylhexyl, 2- Third butylhexyl, 2,2-diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methyldecyl, 2-methyl-2-ethyloctyl, 2-methylundecyl, 10-methylundecyl, 2,2-dimethyldecyl, 2-ethyldecyl, 2- Butyloctyl, diethyloctyl, 2-third butyl-2,2,4-trimethylpentyl, 10-methyldodecyl, 3-methyldodecyl, 4-methyl Yldodecyl, 11-methyldodecyl, 10-ethylundecyl, 12-methyltridecyl, 2-butyldecyl, 2-hexyloctyl, 2-butyl -2-ethyloctyl, 12-methyltetradecyl, 14-methylpentadecyl, 2-butyldodecyl, 2-hexyldecyl, 16-methylheptadecyl, 2,2-Dimethylhexyl, 2-butylhexadecyl, 2-hexyldodecyl, 2,4,10,14-tetramethylpentyl, 18-methyl nineteen amide Base, 3,7,11,15-tetra-methylhexadecyl, 19-methyl eicosyl, etc.

Moreover, in a preferred embodiment of the present invention, in the general formulas (1) and (8), R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ¹⁹ may be the same or different, and have no ring structure A branched carbon group with a carbon number of 10 to 22, or a ring group with no more than 2 branches and a carbon group with a carbon number of 6 to 9.

As such a preferred embodiment, R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ^{19 which} do not contain a ring structure and have a branched C 10-22 acyl group may include 2-methylnonyl Group, 4-methylnonylyl group, 8-methylnonylyl group, 4-ethyloctylyl group, 2-ethyloctylyl group, 2-butylhexylyl group, 2-butylhexylyl group, 2-third butylhexylyl group, 2, 2-Diethylhexyl, 2,2-dimethyloctyl, 3,7-dimethyloctyl, neodecyl, 7-methyldecyl, 2-methyl-2-ethyloctyl , 2-methylundecyl, 10-methylundecyl, 2,2-dimethyldecyl, 2-ethyldecyl, 2-butyloctyl, diethyloctyl, 2 -Third-butyl-2,2,4-trimethylpentylyl, 10-methyldodecyl, 3-methyldodecyl, 4-methyldodecyl, 11-methyl Dodecanoyl, 10-ethylundecyl, 12-methyltridecyl, 2-butyldecyl, 2-hexyloctyl, 2-butyl-2-ethyloctyl, 12-methyl Yltetradecyl, 14-methylpentadecyl, 2-butyldodecyl, 2-hexyldecyl, 16-methylheptadecyl, 2,2-dimethylhexyl , 2-butylhexadecyl, 2-hexyldodecyl, 2,4,10,14-tetramethylpentyl, 18-methyl nonadecyl, 3,7,11,15- Tetramethyl hexadecyl, 19-methyl eicosyl, etc.

In addition, as a preferred embodiment, an acyl group having 6 to 9 carbon atoms having 2 or more branches and not containing a ring structure represented by R ² , R ³ , R ¹⁷ , R ¹⁸ , and R ¹⁹ can be exemplified by 2 ,2-dimethylbutyryl, 3,3-dimethylbutyryl, 2,2-dimethylpentyl, 4,4-dimethylpentyl, 2,2-dimethylhexyl, 2,2,3-trimethylpentanyl, 3,5,5-trimethylhexyl, etc.

In the general formula (1), the group derived from triol represented by X is not particularly limited as long as it desorbs the OH group from the triol, and can be appropriately exemplified by a group selected from the group consisting of glycerol and triol. The trihydric alcohol of the group of methylolpropane and trimethylolethane desorbs the OH group.

In addition, in the general formula (8), the group derived from a tetrahydric alcohol represented by Y is not particularly limited as long as it desorbs the OH group from the tetrahydric alcohol, and can be appropriately exemplified by The tetrahydric alcohol of the group of alcohol, pentaerythritol, erythritol, D-threitol, and L-threitol desorbs the OH group.

In the present invention, it is particularly preferable to use an amphiphilic copolymer containing the structural unit (1).

In a more preferred embodiment of the present invention, the hydrophobic monomer represented by the general formula (1) is the hydrophobic monomer represented by the general formula (15).

The carbon number of the acyl group of R ²⁴ and R ^{25 in} the general formula (15) is 12-22, more preferably 14-20, and particularly preferably 16-20.

In addition, the carbon number of the main chain of the acyl group of R ²⁴ and R ^{25 in} the general formula (15) is preferably 9 to 21, more preferably 12 to 20, and particularly preferably 16 to 18.

In addition, the branch number of the acyl group of R ²⁴ and R ^{25 in} the general formula (15) is preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

Furthermore, in R ^{24 of the} general formula (15) and in the acyl group of R ^25, the larger the position number of the carbon of the main chain of the branch chain bonding, the better. Specifically, the branched chain is preferably bonded to the first to third carbons at the end of the autonomous chain, more preferably the first or second carbon, and particularly preferably the first carbon.

As R ²⁴ and R ²⁵ , specifically, 10-methyl undecyl group, 10-methyl dodecyl group, 11-methyl dodecyl group, 10-ethyl undecyl group, 12-Methyltridecyl, 12-methyltetradecyl, 14-methylpentadecyl, 16-methylheptadecyl, 2,4,10,14-tetramethylpentyl , 18-methyl nineteen amide, 3,7,11,15-tetra-methyl hexadecyl, 19-methyl eicosyl, etc.

In the general formula (15), the group derived from triol represented by Z is not particularly limited as long as it desorbs the OH group from the triol, and can be appropriately exemplified by a group selected from the group consisting of glycerol and triol. The trihydric alcohol of the group of methylolpropane and trimethylolethane desorbs the OH group.

[2] Hydrophilic monomer

As the hydrophilic monomer of the present invention, a polymerizable carboxylic acid and compounds represented by the aforementioned general formulas (2), (9), (10), and (11) can be used.

(2-1) polymerizable carboxylic acid,

In the present invention, specific examples of the polymerizable carboxylic acid or its salt include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, fumaric acid and its sodium, potassium, ammonium, and amine salts. . Among these, acrylic acid, methacrylic acid, and their salts are particularly preferred from the viewpoint of high polymerizability. When the amphiphilic copolymer of the present invention is introduced into a structural unit derived from a polymerizable carboxylate, the polymerizable carboxylic acid may be prepared as a salt in advance to perform a polymerization reaction, or the polymerization reaction may be used to convert the self-polymerizable carboxylate After the acid-derived constituent unit is derivatized as an amphiphilic copolymer, it is neutralized with an alkali to form a salt.

(2-2) Hydrophilic monomer represented by general formula (2)

In the aforementioned general formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁶ represents a hydrogen atom and a carbon atom having 6 to 6 carbon atoms The aromatic hydrocarbon group of 10, the aliphatic hydrocarbon group of 1 to 14 carbon atoms, or the acyl group of 1 to 12 carbon atoms. n represents an integer of 6~40.

Examples of the alkyl group represented by R ⁴ in the general formula (2) include methyl, ethyl, propyl, isopropyl, and cyclopropyl. In the present invention, R ⁶ is preferably a hydrogen atom or a methyl group.

In addition, as the alkylene group represented by R ⁵ , ethyl group, ethyl group, isopropyl group, 2-hydroxypropyl group, 2-hydroxy-2-methyl ethyl group, 2-hydroxy- 1-methylethylidene, etc., but among these, ethylidene or propylidene are preferred, and ethylidene is more preferred.

In addition, among the groups represented by R ⁶ , examples of the aromatic groups having 6 to 10 carbon atoms include phenyl, benzyl, tolyl, and ethylphenyl groups. As the aliphatic hydrocarbon groups having 1 to 14 carbon atoms, Appropriate examples include methyl, ethyl, butyl, tertiary butyl, hexyl, cyclohexyl, octyl, 2-ethylhexyl, lauryl, etc.; as a C 1-12 acyl group, a methyl acyl group can be appropriately exemplified. , Acetyl, propyl, butyl, isobutyl, pentyl, lauryl, etc. Among these, the group represented by R ^{5 is} preferably an aliphatic hydrocarbon group having 1 to 14 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.

Furthermore, n in the general formula (2) is in the range of 6 to 40.

Among the monomers represented by the general formula (2), as the monomer in which R ⁵ is propylene, specifically, polypropylene glycol (9) monoacrylate, polypropylene glycol (13) monoacrylate, poly Propylene glycol (9) monomethacrylate, polypropylene glycol (13) monomethacrylate, etc. Furthermore, the number in parentheses indicates N. Most of these polymers are available as commercial products. Specific examples of these commercially available products include trade names "Blenmer" AP-400, AP-550, AP-800, PP-500, and PP-800 (all manufactured by Nippon Oil & Fats Co., Ltd.).

Among the monomers represented by the general formula (2), as the monomer in which R ⁵ is an ethylidene group, specifically, polyethylene glycol (10) monoacrylate, polyethylene glycol (8) monomer Methacrylate, polyethylene glycol (23) monoacrylate, polyethylene glycol (23) monomethacrylate, methoxypolyethylene glycol (9) acrylate, methoxypolyethylene glycol ( 9) Methacrylate, methoxypolyethylene glycol (23) methacrylate, oleyloxy polyethylene glycol (18) methacrylate, lauryloxy polyethylene glycol (18) acrylate, Lauryloxy polyethylene glycol (10) methacrylate, stearyl polyethylene glycol (30) monomethacrylate, etc.

The above-mentioned hydrophilic monomers can be obtained in a high yield by esterification reaction of corresponding polyethylene glycol, polyethylene glycol monoether, polyethylene glycol monoester with acrylic acid or methacrylic acid chloride or anhydride. In addition, since many commercial products already exist, the commercial products can also be used. As such a commercially available product, specifically, the trade names of Blenmer, AE-400, PE-350, AME-400, PME-400, PME-1000, ALE-800, and PSE-1300 (all of which are Japanese oil ) System) etc.

(2-3) Hydrophilic monomer represented by general formula (9)

As the hydrophilic monomer of the present invention, the hydrophilic monomer represented by the above general formula (9) can also be used.

Specific examples of the hydrophilic monomer represented by the general formula (9) include 2-propenyloxyethyl phosphate choline (APC) and 2-methyl Acryloyloxyethyl phosphate choline (MPC). Such monomers can be synthesized by the following method described in Polymer Journal, Vol22, No. 5, for example.

<synthesis method>

Reacting 2-bromoethylphosphoryl dichloride with 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate to obtain 2-methacryloxyethyl-2'-bromoethyl phosphoric acid or 2- After acryloyloxyethyl-2'-bromoethyl phosphoric acid, these compounds are reacted with triethylamine in methanol.

(2-4) Hydrophilic monomer represented by general formula (9)

As the hydrophilic monomer of the present invention, the hydrophilic monomer represented by the general formula (10) can also be used.

Among the hydrophilic monomers represented by the general formula (10), the reducing sugar that is a group that removes hydrogen from the hydroxyl group at the 1-position of the reducing sugar represented by GO- can be specifically selected from the group consisting of glucose and mannose. Groups of monosaccharides such as sugar, galactose, arabinose, xylose, ribose, disaccharides such as maltose, lactose, cellobiose, trisaccharides such as maltotriose, and oligosaccharides such as maltooligosaccharide One or two or more, among which one or two or more selected from the group consisting of glucose, galactose, arabinose, xylose, ribose, maltose, lactose, and cellobiose is preferred, and glucose is particularly preferred. Further, as the monomer represented by the general formula (10), glucosyloxyethyl methacrylate (hereinafter abbreviated as GEMA) or glucosyloxyethyl acrylate (hereinafter abbreviated as GEA) is preferred.

(2-5) Hydrophilic monomer represented by general formula (11)

As the hydrophilic monomer of the present invention, the hydrophilic monomer represented by the aforementioned general formula (11) can also be used.

In the monomer of the general formula (11), the amino acid as the amino acid residue represented by R ²³ is not particularly limited as long as it is a generally known amino acid, and specifically, glycine can be exemplified. Acid, alanine, glutamic acid, lysine, arginine, etc. Among these, since the skin barrier recovery effect of the obtained amphiphilic copolymer is good, the amino acid residue is particularly preferable.

In addition, the polyamine of the polyamine residue represented by R ²³ means an amine having two or more amine groups that can be substituted with an alkyl group in the same molecule. Specifically, a diamine, triamine, tetraamine or An amine in which the hydrogen atom of the amine group is substituted with an alkyl group. Among these, from the viewpoint that the use of the skin-derived external preparation containing the obtained amphiphilic copolymer is particularly good, diamine is preferable, and as a particularly good specific example, from the viewpoint of easy availability of raw materials at the time of synthesis , Ethylenediamine, 1,4-diamino-n-butane, 1,6-diamino-n-hexane, etc. are mentioned.

The amine alcohol as the amine alcohol residue represented by R ²³ means a compound having an alkyl-substituted amine group and an alcoholic hydroxyl group in the same molecule. The amino alcohol is not particularly limited as long as it is generally known, and specific examples include ethanolamine, triethylaminoethanol, and the like.

The salt of the monomer represented by the general formula (11) is not particularly limited, and specifically, there can be exemplified sodium salts, potassium salts, ammonium salts, amine salts and the like neutralized with an acid moiety, or Partially acid neutralized hydrochloride, sulfate, nitrate, phosphate, citrate, oxalate, carbonate, etc. When the amphiphilic copolymer of the present invention is introduced into the structural unit derived from the monomer salt represented by the general formula (11), the monomer represented by the general formula (11) may be prepared as a salt in advance and subjected to a polymerization reaction, You can also use polymerization to The structural unit derived from the monomer represented by the general formula (11) is derived into an amphiphilic copolymer, and then neutralized to form a salt.

As a specific example of the salt of the monomer represented by the general formula (11), compounds 1 to 11 and salts thereof can be appropriately exemplified.

The hydrophilic monomer represented by the general formula (11), for example, as shown in the aforementioned reaction formulas (1) and (2), can be obtained by an esterification reaction using (meth)acrylic acid or (meth)acryloyl chloride , Amidation reaction synthesis.

As described above, in the present invention, as the hydrophilic polymer, the aforementioned general formulas (2), (9), (10), and (11) can be used.

In a preferred embodiment of the present invention, the amphiphilic copolymer includes a structural unit (2) derived from the aforementioned general formula (2).

[3] Amphiphilic copolymer

In the present invention, an amphiphilic copolymer having a structural unit (1) and a structural unit (2) is particularly applicable. Furthermore, it is more preferable to use an amphiphilic copolymer having a structural unit (15) and a structural unit (2).

Among such acrylic amphiphilic copolymers, (methoxy methacrylate PEG-23/diisostearic acid glyceryl methacrylate) copolymer can be particularly preferably used.

By containing such an acrylic amphiphilic copolymer, the moisture retention and flexibility of the coating can be improved.

(Methoxy methacrylate PEG-23/diisostearic acid glyceryl methacrylate) copolymer, as the structural unit (i), is mainly contained from the hydrophobic monomer represented by the aforementioned general formula (15), R ²⁴ and R ²⁵ are structural units (i) derived from a hydrophobic monomer of 16-methylheptadecyl group.

Moreover, as a structural unit (j), it is mainly comprised from the hydrophilic monomer represented by the said general formula (2), R ⁴ is a methyl group, R ⁵ is an ethyl group, R ⁶ is a methyl group, and n is 23 Structural unit (j) derived from a hydrophilic monomer.

As the amphiphilic copolymer of the present invention, in addition to the above-mentioned copolymers, existing copolymers can also be used. Specifically, as the amphiphilic copolymer, conventional copolymers listed below can be used.

That is, polyquaternium-51 (copolymer containing 2-methacryloyloxyethyl phosphate choline and butyl methacrylate at a molar ratio of about 8:2), polyquaternium -61 (copolymer containing 2-methacryl oxyethyl phosphate choline and stearyl methacrylate at a molar ratio of about 3:7), (glyceryl methacrylate ethyl methacrylate/methyl Stearyl Acrylate) copolymer (weight average of glyceryl-N-(2-methacryloxyethyl)carbamate and stearyl methacrylate in a molar ratio of about 6:4 (Copolymer with molecular weight of about 40,000), PEG/PPG/polybutanediol-8/5/3 glycerin, (hydrolyzed silk protein/PG propylmethylsilanediol) cross-linked polymer (the N-[2 -Hydroxy-3-[3-(hydroxymethylsilyl)propoxy]propyl]silicone hydrolyzed copolymer), (Eicosanedioic acid/tetradecanedioic acid) polyglycerol ester-10 (Contains oligomeric esters of dibasic acid of eicosanedioic acid, tetradecanedioic acid and polyglycerol with an average degree of polymerization of 10), (glycerol/butylene oxide) copolymer stearic ether (in Stearyl alcohol reacts glycidol and tetrahydrofuran at the same time, and addition polymerizes the polymer with HLB of 18.0), polyquaternium-7 (copolymer of dimethyldiallylammonium chloride and propylene amide) ), polyquaternium-39 (acrylic acid, dimethyldiallyl ammonium chloride and acrylamide terpolymer), (acrylic acid Na/acryl dimethyl taurine) copolymer (sodium acrylate and Existing copolymers such as copolymers of sodium propionyl dimethyl taurine).

Among these, especially polyquaternium-51, polyquaternium-61, (glyceryl methacrylate ethyl ester/stearyl methacrylate) copolymer can be suitably exemplified.

In the present invention, the proportion of the structural units (i) of the amphiphilic copolymer in the total structural units is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, and 10 to 30% by mass.

By making the ratio of the structural unit (i) of the amphiphilic copolymer within the aforementioned range, the moisture retention and flexibility of the coating of the present invention can be improved.

In the present invention, the proportion of the structural units (j) of the amphiphilic copolymer in the total structural units is preferably 50 to 99% by mass, more preferably 60 to 95% by mass, and 70 to 90% by mass.

By making the ratio of the structural unit (j) of the amphiphilic copolymer into the aforementioned range, the moisture retention and flexibility of the coating of the present invention can be improved.

In the present invention, the mass ratio of the constituent unit (i) to the constituent unit (j) constituting the amphiphilic copolymer is preferably 5:95 to 50:50, further preferably 10:90 to 45:55 , Better is 20:80~40:60, especially good is 25:75~35:65.

By setting the mass ratio of the structural unit (i) and the structural unit (j) of the amphiphilic copolymer to the aforementioned range, the moisture retention and flexibility of the coating of the present invention can be improved.

In the present invention, the molar ratio of the constituent unit (i) and the constituent unit (j) constituting the amphiphilic copolymer is preferably 8:92 to 62:38, and more preferably 15:85 to 57: 43, better is 29:71~52:48, especially good is 35:65~46:54.

By setting the molar ratio of the structural unit (i) and the structural unit (j) of the amphiphilic copolymer to the aforementioned range, the moisture retention and flexibility of the coating of the present invention can be improved.

In the present invention, the average molecular weight of the amphiphilic copolymer is preferably 20,000 to 110,000, more preferably 20,000 to 80,000, more preferably 30,000 to 80,000, still more preferably 40,000 to 70,000, and particularly preferably 50,000 70,000, further preferably 57000~66000.

By making the molecular weight of the amphiphilic copolymer into the aforementioned range, the elasticity of the coating of the present invention can be improved, and the stickiness can be suppressed.

Here, the average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by GPC.

<1-2> Marine

The island particles are dispersed in the sea phase of the aqueous gel. In the present invention, the aqueous gel system is formed using water-soluble polymers and/or salts thereof and water hydrated in the water-soluble polymers.

The water-soluble polymer and/or its salt that forms an aqueous gel is not particularly limited as long as the phase containing the amphiphilic polymer is dispersed as the island particles, and it can be preferably selected from the group consisting of acrylic water-soluble polymers. One or more than two kinds of water-soluble polymers and/or salts thereof in the group of substances, water-soluble polypeptides and water-soluble polysaccharides.

As the acrylic water-soluble polymer, a non-crosslinkable acrylic polymer or a crosslinkable acrylic copolymer can be particularly exemplified. In addition, as the non-crosslinkable acrylic polymer, sodium polyacrylate is particularly exemplified, and as the aforementioned crosslinkable acrylic copolymer, sodium polyacrylate and (acrylate/alkyl acrylate (C10-30)) are particularly exemplified. Crosslinked polymers.

As the aforementioned water-soluble polypeptide, sodium polyglutamine is particularly exemplified.

As the aforementioned water-soluble polysaccharide, three gums or tremella polysaccharides are particularly exemplified. It is especially applicable to Sanxian gum as a water-soluble polysaccharide.

By using such a water-soluble polymer and/or its salt, the moisture retention and flexibility of the coating of the present invention can be improved.

<1-3> Island structure

The film of the present invention has a sea-island structure in which an island phase containing an amphiphilic copolymer is dispersed in a sea phase containing an aqueous gel.

In the coating with the island structure of the present invention, the area ratio of the sea phase to the island phase is preferably 2:8~10:1, more preferably 3:7~9:1, and particularly preferably 6:4~7 : 3.

The film of the present invention having an area ratio of the sea phase to the island phase within the aforementioned range has excellent elasticity, less stickiness, and excellent moisturization and flexibility.

In a preferred embodiment of the present invention, the average long axis to short axis ratio of the island particles is preferably 0.6 or more, more preferably 0.7 or more, particularly preferably 0.8 or more, and most preferably 0.9 or more.

By setting the average long axis and short axis ratio of the island particles to the aforementioned range, the moisture retention and flexibility of the coating of the present invention can be improved.

In addition, the average long axis to short axis ratio can be measured by observing the composition with a microscope. Specifically, the composition can be obtained by observing the composition with a microscope, measuring the long-axis and short-axis ratios of 100 island particles, and adding them to the average.

Furthermore, in a preferred embodiment of the present invention, the ratio of the major axis to the minor axis of all the island particles contained in the coating is less than 0.6, more preferably less than 0.7, and particularly preferably the ratio of island particles less than 0.8 is 10% or less.

Furthermore, in a more preferred embodiment of the present invention, the ratio of island particles having a long axis to short axis ratio of all island particles contained in the composition of less than 0.8 is 5% or less, more preferably 1% or less.

The film of this embodiment has better moisture retention and flexibility.

In a preferred embodiment of the present invention, the island particles having an average particle diameter of 0.5 to 10 μm, and more preferably, the number of island particles having an average particle diameter of 1 to 5 μm have a particle size distribution of 80% or more.

Furthermore, in a more preferred embodiment of the present invention, the number of island particles having an average particle diameter of 1 to 5 μm has a particle size distribution of 85% or more, more preferably 90% or more.

By making the particle size distribution of the island particles with such a small particle size into the aforementioned range, the moisture retention and flexibility of the coating of the present invention can be further improved.

Furthermore, the average particle size of island particles can be measured by observing the composition with a microscope. Specifically, the composition can be obtained by observing the composition with a microscope, measuring the long axis and short axis of the island particles, and adding them to the average.

The coating film of the present invention may contain any components commonly used in external preparations for skin. Examples of such components include oils, waxes, hydrocarbons, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, surfactants, polyols, moisturizing ingredients, and thickening Agents, powders, inorganic pigments, organic pigments, organic powders, ultraviolet absorbers, lower alcohols, vitamins, polymers with biosimilar structures, etc.

Examples of oils and waxes include Australian walnut oil, avocado oil, corn oil, olive oil, rapeseed oil, sesame oil, castor oil, safflower seed oil, cottonseed oil, jojoba oil, coconut oil, palm oil Oil, liquid lanolin, hardened coconut oil, hardened oil, wood wax, hardened castor oil, bee Wax, candelilla wax, carnauba wax, insect wax, lanolin, reduced lanolin, hard lanolin, jojoba wax, etc.; as hydrocarbons, for example, flowing paraffin, squalane, isooctadecane , Ozokerite, paraffin wax, mineral wax, petrolatum, microcrystalline wax, etc.; as the higher fatty acids, for example, oleic acid, isostearic acid, lauric acid, myristic acid, palmitic acid, stearic acid, twenty Diacids, undecylenic acid, etc.; as higher alcohols, for example, cetyl alcohol, stearyl alcohol, isostearyl alcohol, eicosanediol, octyldodecanol, myristyl alcohol, cetearyl Fatty alcohols and the like; as synthetic ester oils, for example, cetyl isooctanoate, isopropyl myristate, cetyl isostearate, diisopropyl adipate, di-2 sebacate -Ethylhexyl ester, cetyl lactate, diisostearyl malate, ethylene glycol di-2-ethylhexanoate, neopentyl glycol didecanoate, propane tri-2-heptyl undecanoate Alcohol ester, glycerol tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, tetra-2-ethylhexyl Pentaerythritol acid ester, etc.; Examples of silicone oils include chain polysiloxanes such as dimethyl polysiloxane, methylphenyl polysiloxane, diphenyl polysiloxane, etc. , Cyclic polysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecylcyclohexanesiloxane, amine modified polysiloxane, polyether Silicone oils such as modified polysiloxanes, alkyl modified polysiloxanes, fluorine modified polysiloxanes and other modified polysiloxanes.

The surfactants may be any of anionic surfactants and nonionic surfactants.

Examples of anionic surfactants include fatty acid soaps (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, and alkyl sulfate triethanolamine ether. Examples of nonionic surfactants include, for example. , Sorbitan fatty acid esters (sorbitan monostearate, sorbitan sesquioleate, etc.), glycerin fatty acids (glycerol monostearate, etc.), propylene glycol fatty acid esters (Propylene glycol monostearate, etc.), hardened castor oil derivatives, glycerol alkyl ether, POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate Alcohol anhydride, etc.), POE sorbitol fatty acid esters (POE-sorbitol monolaurate, etc.), POE glycerol fatty acid esters (POE-glycerol monoisostearate, etc.), POE fatty acid esters (Polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE2-octyl dodecyl ether, etc.), POE alkyl phenyl ethers (POE nonyl phenyl ether, etc.), Planic type, POE‧POP alkyl ethers (POE‧POP2-decyltetradecyl ether, etc.), special windows, POE castor oil‧hardened castor oil derivatives (POE castor oil, POE hardened castor oil, etc.), Sucrose fatty acid ester, alkyl glucoside, etc.

Examples of the polyhydric alcohols include polyethylene glycol, erythritol, xylitol, propylene glycol, dipropylene glycol, isopentyl glycol, 1,2-pentanediol, and 2,4-hexanediol. 1,2-hexanediol, 1,2-octanediol, etc.; as a moisturizing component, for example, sodium pyrrolidone carboxylate, lactic acid, sodium lactate, etc.; as a thickener, for example, off Huadou gum, quince seeds, carrageenan, galactosan, acacia, pectin, mannan, starch, cardlan gum, methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, Methyl hydroxypropyl cellulose, chondroitin sulfate, dermatan sulfate, glycogen, acetoheparin sulfate, hyaluronic acid, sodium hyaluronate, tragacanth gum, keratan sulfate, chondroitin, mucopolysaccharide sulfate, hydroxyethyl Guanhua bean Gum, Carboxymethyl Guanhua Gum, Glucan, Keratan Sulfate, Locust Bean Gum, Succinyl Glycan, Tonic Acid, Chitin, Chitosan, Carboxymethyl Chitosan, Watercress, Polyvinyl Alcohol , Polyvinylpyrrolidone, carbopol, polyethylene glycol, bentonite, etc.

Examples of powders include mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, silicic anhydride (silica), aluminum oxide, and barium sulfate that can be treated on the surface; examples of inorganic pigments include, for example, , Can include iron dan, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, cyanine, titanium oxide, zinc oxide, etc. which can be treated on the surface; as organic pigments, mica can be treated on the surface Pearlescent agents such as titanium, fish foil, bismuth oxychloride, red 202, red 228, red 226, yellow 4, blue 404, yellow 5, red 505, Red No. 230, Red No. 223, Orange No. 201, Red No. 213, Yellow No. 204, Yellow No. 203, Blue No. 1, Green No. 201, Purple No. 201, Red No. 204, etc.; as organic powders, can be mentioned For example, polyethylene powder, polymethyl methacrylate, nylon powder, organic polysiloxane elastomer, etc.

Examples of the ultraviolet absorbers include p-aminobenzoic acid-based ultraviolet absorbers, o-aminobenzoic acid-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, cinnamic acid-based ultraviolet absorbers, and benzophenone-based ultraviolet absorbers. UV absorber, sugar-based UV absorber, 2-(2'- Hydroxy-5'-tert-butyloctylphenyl)benzotriazole, 4-methoxy-4'-tert-butyldibenzoylmethane, etc.; as the lower alcohols, for example, ethanol , Isopropanol, phenoxyethanol, etc.; as vitamins, particularly exemplified examples are vitamin A or its derivatives, vitamin B6 hydrochloride, vitamin B6 tripalmitate, vitamin B6 dicaprylate, vitamin B2 or Vitamin B, α-tocopherol, β-tocopherol, γ-tocopherol, vitamin E acetate, etc., vitamin E, vitamin D, vitamin D, vitamin D, vitamin B12, vitamin B12 or its derivatives H, pantothenic acid, pantethine, pyrroloquinoline quinone, etc.

As the polymer having a biosimilar structure, for example, polymethacryloyl lysine, polyglycosylethyl methacrylate, and the like are particularly exemplified.

In the present invention, the content of oils such as oils, waxes, hydrocarbons, higher fatty acids, higher alcohols, synthetic ester oils, and silicone oils is preferably 10% by mass or less, and more preferably It is 5% by mass or less, more preferably 2.5% by mass or less, even more preferably 2% by mass or less, particularly preferably 1% by mass or less, and even more preferably 0.5% by mass or less.

In addition, in a preferred embodiment of the present invention, no oil agent is contained.

The coating film having the sea-island structure of the present invention can exert a feeling of use such as milk containing oil, regardless of whether the aqueous component is the main component.

Therefore, the film having the sea-island structure of the present invention can be in an oil-free form.

Furthermore, in the present invention, the content of the surfactant is preferably 10% by mass or less, more preferably 5% by mass or less, more preferably 2.5% by mass or less, still more preferably 2% by mass or less, and particularly preferably 1 mass% or less, further preferably 0.5 mass% or less.

Furthermore, in a preferred embodiment of the present invention, no surfactant is contained.

The coating of the present invention can form a stable island structure regardless of whether or not it contains a surfactant.

Therefore, the film having the sea-island structure of the present invention can be in a form free of surfactant.

<2> Film-forming composition

The present invention also relates to a composition that can be formed on the skin by coating the skin with the sea island structure of the present invention as described above.

The composition of the present invention contains the above-mentioned amphiphilic copolymer, water-soluble polymer and/or its salt, and water.

By applying to the skin and evaporating the water in the composition, the amphiphilic copolymer and the water-soluble polymer can be separated. As a result of this phase separation, the coating of the present invention is formed on the skin. Furthermore, after phase separation, the water and polyols in the composition enter the aqueous gel formed by the water-soluble polymer.

The composition of the present invention will be described in further detail below. In addition, regarding the composition of the present invention, the matters related to the coating film of the present invention described in the above item <1> can be applied.

In the composition of the present invention, the content of the amphiphilic copolymer is preferably 0.01 to 10% by mass, further preferably 0.5 to 7% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.5 to 3% by mass.

According to the composition of the present invention in which the content of the amphiphilic copolymer is within the aforementioned range, a film having excellent elasticity and less stickiness can be formed on the skin.

In the present invention, the proportion of the aforementioned water-soluble polymer in the entire composition is preferably 0.001 to 10% by mass, further preferably 0.005 to 5% by mass, more preferably 0.01 to 1% by mass, and particularly preferably 0.05~0.5% by mass.

According to the composition of the present invention in which the content of the water-soluble polymer is in the aforementioned range, a coating film having excellent moisture retention and flexibility can be formed on the skin.

In a preferred embodiment of the present invention, the mass ratio of the content of the water-soluble polymer and the amphiphilic copolymer is preferably 1:100~1:2, further preferably 1:50~1:5, More preferably, it is 1:30~1:10, and especially good is 1:25~1:15.

According to the composition of the present invention in which the mass ratio of the water-soluble polymer and the amphiphilic copolymer is within the aforementioned range, a highly uniform coating can be formed.

In the present invention, it is preferable to include a polyol that promotes and inhibits the separation of the sea phase and the island phase.

That is, in a preferred embodiment of the present invention, it contains a polyol (hereinafter also referred to as a promoting polyol) that promotes the phase separation of the aqueous gel and the amphiphilic copolymer and/or inhibits the aqueous gel and Phase separated polyol of amphiphilic copolymer (hereinafter also referred to as inhibitory polyol). In addition, it is particularly preferable to include both the promoting polyol and the inhibiting polyol.

According to the composition of the present invention containing such a polyhydric alcohol, a film having a sea-island structure with high uniformity can be formed on the skin.

As the accelerating polyol, a polyol which is mixed with an aqueous solution of a nonionic surfactant having a polyether chain in the hydrophilic portion and raised to the cloud point of the aqueous solution is particularly exemplified. As such a promoting polyol, 1,3-butanediol and polyethylene glycol are particularly exemplified.

By using such a polyol, a more uniform coating can be formed.

In the present invention, the content of the promoting polyol in the entire composition of the present invention is preferably 0.1 to 30% by mass, further preferably 1 to 25% by mass, more preferably 3 to 20% by mass, and particularly preferably 5~15% by mass.

By making the content of the promoting polyol in the entire composition of the present invention within the aforementioned range, the uniformity of the formed film can be further improved.

As an inhibitory polyol, a polyol in which the cloud point of the aqueous solution is lowered by mixing with an aqueous solution of a nonionic surfactant having a polyether chain in the hydrophilic portion is particularly exemplified. Examples of such inhibitory polyols include glycerin, diglycerin, sorbitol, and maltitol.

By using such a polyol, a more uniform coating can be formed.

The content of the inhibitory polyol in the entire composition of the present invention is preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass, more preferably 5 to 20% by mass, and particularly preferably 8 to 15% by mass .

By making the content of the promoting polyol into the aforementioned range, the uniformity of the formed film can be further improved.

Furthermore, in the present invention, the cloud point refers to the phase separation caused by temperature change in a transparent or translucent liquid, and the result becomes The opaque temperature means, in particular, the temperature at which the solute and water begin to separate when the aqueous solution of the nonionic surfactant is heated.

Whether to increase or decrease the cloud point of an aqueous solution of a nonionic surfactant having a polyether chain in the hydrophilic part can be specifically confirmed by the following method.

An aqueous solution of a nonionic surfactant having a polyether chain in the hydrophilic part is heated, and the temperature at which the aqueous solution starts to be cloudy, that is, the cloud point is recorded. Next, a polyol was added to this aqueous solution and the mixture was heated, and the cloud point was similarly recorded.

When the cloud point of the aqueous solution after the addition is higher than that of the aqueous solution before the addition of the polyol, the polyol added is evaluated as "increasing the cloud point of the aqueous solution".

Conversely, when the cloud point of the aqueous solution after the addition is lower than that of the aqueous solution before the addition of the polyol, the polyol added is evaluated as "decrease the cloud point of the aqueous solution".

As the nonionic surfactant having a polyether chain in the hydrophilic part used for the measurement of the cloud point, a nonionic surfactant having polyethylene glycol in the hydrophilic part can be particularly exemplified.

As such a nonionic surfactant, specifically, polyoxyethylene oil ether (POE(n)OE, n=3,10,15,20,23) (manufactured by NIHON EMULSION), POE( 20) Sorbitan monostearate (manufactured by Toho Chemical Co., Ltd.), POE (20) glycerin monostearate (manufactured by Riken Vitamin Co., Ltd.), POE (10) monostearate (Sunlight Chemicals Co., Ltd.), polyglycerol (6) monolaurate (Sakamoto Pharmaceutical Co., Ltd.).

In the present invention, the mass ratio of the promoting polyol to the inhibiting polyol is preferably 10:1 to 1:10, more preferably 6:1 to 1:5, and even more preferably 4:1 to 1: 3. Further better is 3.5:1~1:2.5, and particularly good is 1.6:1~1:1.

By setting the mass ratio of the promoting polyol and the inhibiting polyol to the aforementioned range, it is possible to provide a composition capable of forming a coating film having a high-stability sea island structure.

In the present invention, the ratio of the total mass of the promoting polyol and the suppressing polyol to the content of the amphiphilic copolymer is 5:1 to 20:1, more preferably 7:1 to 15:1. It is preferably 8:1~12:1.

By making the ratio of the total mass of the promoting polyol and the suppressing polyol to the mass of the amphiphilic copolymer into the aforementioned range, it is possible to provide a composition with a sea island structure with high stability.

Furthermore, in the present invention, the ratio of the total mass of the promoting polyol and the suppressing polyol to the total mass of the amphiphilic copolymer and the water-soluble polymer is 5:1 to 20:1, more preferably 7: 1~15:1, especially good is 8:1~12:1.

By making the ratio of the total mass of the promoting polyol and the suppressing polyol to the mass of the amphiphilic copolymer into the aforementioned range, it is possible to provide a composition with a sea island structure with high stability.

In a preferred embodiment of the present invention, the content of the promoting polyol in the total amount of the three components of the promoting polyol, the inhibiting polyol and the amphiphilic copolymer is preferably 10 to 80% by mass, further It is preferably 20 to 70% by mass, more preferably 30 to 70% by mass, even more preferably 40 to 60% by mass, and particularly preferably 40 to 55% by mass.

By setting the content of the promoting polyol to the aforementioned range, it is possible to prevent precipitation in the composition and to improve the stability of the composition. In addition, as in the composition of the aforementioned form, a coating having excellent moisture retention and flexibility can be formed.

Furthermore, in a preferred embodiment of the present invention, the content of the inhibitory polyol in the total amount of the three components of the promoting polyol, the inhibitory polyol and the amphiphilic copolymer is preferably 10 to 80% by mass It is further preferably 20 to 70% by mass, more preferably 30 to 60% by mass, and particularly preferably 35 to 50% by mass.

By setting the content of the inhibitory polyol within the aforementioned range, precipitation of the composition can be prevented, and the stability of the composition can be improved. In addition, as in the composition of the aforementioned form, a coating having excellent moisture retention and flexibility can be formed.

Furthermore, in a preferred embodiment of the present invention, the content of the amphiphilic copolymer in the total amount of the three components of the promoting polyol, the inhibiting polyol and the amphiphilic copolymer is preferably 1 to 50 The mass% is further preferably 3-20 mass%, more preferably 5-15 mass%, and particularly preferably 8-12 mass%.

By making the content of the amphiphilic copolymer into the aforementioned range, it is possible to provide a composition having viscosity that is easy to apply to the skin. In addition, as in the composition of the aforementioned form, a coating having excellent moisture retention and flexibility can be formed.

In a preferred form of the present invention, in the total amount of the three components of the promoting polyol, the inhibiting polyol, and the amphiphilic copolymer, the content of the promoting polyol is 20 to 70% by mass, and the inhibiting polyol The content of alcohol is 20 to 70% by mass, and the content of amphiphilic copolymer is 5 to 20% by mass.

By becoming such an embodiment, the stability of the composition can be improved.

In addition, by combining the total content of the three components of the promoting polyol, the suppressing polyol and the amphiphilic copolymer, the content of the promoting polyol, the content of the inhibiting polyol and the content of the amphiphilic copolymer By adjusting to the aforementioned range, the long-axis to short-axis ratio and average particle diameter of the island particles of the film formed by the composition of the present invention can be adjusted to the preferred ranges described in the above items <1-3>.

The composition of the present invention can be produced by stirring and mixing the raw materials at room temperature.

The water content of the composition of the present invention is preferably 60 to 99% by mass, more preferably 70 to 95% by mass, and particularly preferably 80 to 90% by mass.

By applying the composition of the present invention having a water content in the aforementioned range to the skin, the coating of the present invention can be easily formed on the skin.

<3> Method of forming a film on the skin

The present invention also relates to a method of forming the above-mentioned coating of the present invention on the skin.

The method of the present invention is characterized in that the composition of the present invention is applied to the skin. By using the water in the coating evaporation composition, the aqueous gel formed by the water-soluble polymer and the amphiphilic copolymer can be separated. As a result of this phase separation, a film having the sea-island structure of the present invention can be formed on the skin.

In the present invention, an aqueous solution containing a polyol that promotes the phase separation of the amphiphilic copolymer and the aqueous gel and/or a polyol that inhibits the phase separation of the aqueous gel and the amphiphilic copolymer is preferably used .

By using such an aqueous solution, a uniform coating can be formed on the skin.

Furthermore, in the composition of the present invention, the content of oils such as oils, waxes, hydrocarbons, higher fatty acids, higher alcohols, synthetic ester oils, silicone oils, etc. is preferably 2% by mass Below, it is more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

In addition, in a preferred embodiment of the present invention, no oil agent is contained.

In the composition of the present invention, the content of the surfactant is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

Furthermore, in a preferred embodiment of the present invention, no surfactant is contained.

The preferred forms of the composition and coating of the method of the present invention are as described in the above items <1> and <2>.

[Example] <1> Synthesis of hydrophobic monomers

The following shows a production example of the hydrophobic monomer represented by the general formula (1).

(Production Example 1) Synthesis of glycerin monoacrylate

In a 3-L 4-neck flask, add 79.5 g of R)-(+)-2,2-dimethyl-1,3-dioxolane-4-methanol (manufactured by Tokyo Chemical Industry Co., Ltd.), acrylic acid 258.0g of methyl ester and 3.7g of tetramethoxy titanium. Then, the reaction liquid was stirred, and while introducing nitrogen into the liquid, the transesterification reaction was carried out at 105 to 110° C. for 2.5 hours. After the reaction was completed, ketal acrylate 1 (intermediate 1) was obtained by fractional distillation using vacuum distillation.

In a 3-liter 4-neck flask, 90.2 g of water, 28.4 ml of cation exchange resin RCP160M (manufactured by Mitsubishi Chemical), and 94.2 g of Intermediate 1 were added. Then, the reaction liquid was stirred, and while introducing nitrogen into the liquid, the ketal deketalization reaction was performed at 24°C for 27 hours. After the reaction was completed, the cation exchange resin was filtered from the reaction solution, and the filtered reaction solution was washed 6 times with 100 ml of hexane to remove unreacted raw materials, and 200 ml of ethyl acetate was added to the aqueous layer to extract the product. Then, the ethyl acetate extract was distilled off under reduced pressure (800 Pa) at 40° C. or lower to obtain ethyl glycerol monoacrylate.

(Production Example 2) Synthesis of trimethylolpropane monoacrylate

Step (1): In an eggplant-shaped flask equipped with a calcium tube, a cooling tube and a Dean-Stark separator, add 145.7 g of trimethylolpropane, 300 ml of acetone, 3 g of p-toluenesulfonic acid monohydrate and 300 ml of petroleum ether. Heat to reflux in an oil bath set at 50°C. After 12 hours, after confirming that there was no newly formed moisture, the reaction mixture was cooled to room temperature. Next, 3 g of sodium fatty acid was added and stirred for 30 minutes, and petroleum ether and acetone were distilled off with an evaporator. The obtained crude product was distilled under reduced pressure to obtain ketalized trimethylolpropane (intermediate 2).

Step (2): In a 3-L 4-neck flask, 104.8 g of Intermediate 2 obtained in step (1), 258.0 g of methyl acrylate, and 3.7 g of tetramethoxytitanium were added. Then, the reaction liquid was stirred, and while introducing nitrogen into the liquid, the transesterification reaction was carried out at 105 to 110° C. for 2.5 hours. After the completion of the reaction, acetalized trimethylolpropane acrylate (intermediate 3) was obtained by fractional distillation using vacuum distillation.

Step (3): In a 3-L 4-neck flask, 90.2 g of water, 28.4 ml of cation exchange resin RCP160M (manufactured by Mitsubishi Chemical), and 115.3 g of intermediate 3 obtained in step (2) were added. Then, the reaction liquid was stirred, and while introducing nitrogen into the liquid, the ketal deketalization reaction was performed at 24°C for 27 hours. After the reaction was completed, the cation exchange resin was filtered from the reaction solution, and the filtered reaction solution was washed 6 times with 100 ml of hexane to remove unreacted raw materials, and 200 ml of ethyl acetate was added to the aqueous layer to extract the product. Then, the ethyl acetate extract was distilled off under reduced pressure (800 Pa) at 40° C. or lower to obtain ethyl trimethylolpropane monoacrylate.

(Production Example 3) Synthesis of trimethylolpropane monomethacrylate

In addition to the addition amount of trimethylolpropane, methyl acrylate (acrylate) of production example 2, intermediate obtained in step (1), and addition amount of intermediate obtained in step (2), as shown in Table 1. Except for the change shown, the same operation as in Production Example 2 was carried out to synthesize trimethylolpropane monomethacrylate. Table 1 shows the triol and the amount thereof, the intermediate obtained in step (1) and the amount thereof, and the intermediate obtained in step (2) and the amount thereof.

(Production Example 4) Production Example 1 of the hydrophobic monomer represented by the general formula (1)

In a reaction vessel equipped with a stirrer and a cooling tube, measure 28.4g of 16-methylheptadecanoic acid (manufactured by Sigma-Aldrich) and 35.7g of thiosulfonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 200ml of benzene, and mix . After stirring and refluxing for 4 hours, purification by vacuum distillation was performed to obtain 16-methylheptadecyl chloride.

In a reaction vessel equipped with a stirring device, 16.0 g of glycerin monomethacrylate "Blenmer GLM" (manufactured by Nippon Oil & Fats Co., Ltd.) and 30.0 g of triethylamine were dissolved in 300 ml of tetrahydrofuran. The resulting solution was ice-cooled, and while stirring, a solution prepared by dissolving 60.6 g of 16-methylheptadecyl chloride obtained above in 100 ml of tetrahydrofuran was added dropwise over 2 hours. After the dropwise addition was completed, the resulting white precipitate was filtered, and tetrahydrofuran and triethylamine were removed from the filtrate using a rotary evaporator to obtain a product. By NMR measurement, it was confirmed that the obtained compound was a hydrophobic monomer (hydrophobic monomer 1) derived from a necessary structural unit of the copolymer of the present invention represented by the following formula (29).

Hydrophobic monomer 1

(Production Example 5) Production Example 2 of the hydrophobic monomer represented by the general formula (1)

In a reaction vessel equipped with a stirrer and a cooling tube, 25.6 g of 2-hexadecanoic acid (manufactured by Sigma-Aldrich) and 35.7 g of thiosulfonyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 200 ml of benzene were weighed and mixed with stirring. After stirring and refluxing for 4 hours, purification by vacuum distillation was performed to obtain 2-hexadecyl chloride.

In a reaction vessel equipped with a stirring device, 16.0 g of glycerin monomethacrylate "Blenmer GLM" (manufactured by Nippon Oil & Fats Co., Ltd.) and 30.0 g of triethylamine were dissolved in 300 ml of tetrahydrofuran. The resulting solution was ice-cooled, and while stirring, a solution prepared by dissolving 55.0 g of 2-hexadecanoyl chloride obtained above in 100 ml of tetrahydrofuran was added dropwise over 2 hours. After the dropwise addition was completed, the resulting white precipitate was filtered, and tetrahydrofuran and triethylamine were removed from the filtrate using a rotary evaporator to obtain a product. By NMR measurement, it was confirmed that the obtained compound was a hydrophobic monomer (hydrophobic monomer 2) derived from a necessary structural unit of the copolymer of the present invention represented by the following formula (30).

Hydrophobic monomer 2

(Production Example 6) Part 3 of Production Examples of Hydrophobic Monomers Represented by General Formula (1)

In a reaction vessel equipped with a stirrer and a cooling tube, measure 28.4 g of 9-methylheptadecanoic acid (manufactured by Sigma-Aldrich) and 35.7 g of thionyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 200 ml of benzene, and mix by stirring . After stirring and refluxing for 4 hours, purification by vacuum distillation was performed to obtain 9-methylheptadecyl chloride.

In a reaction vessel equipped with a stirring device, 16.0 g of glycerin monomethacrylate "Blenmer GLM" (manufactured by Nippon Oil & Fats Co., Ltd.) and 30.0 g of triethylamine were dissolved in 300 ml of tetrahydrofuran. The resulting solution was ice-cooled, and a solution prepared by dissolving 60.6 g of 9-methylheptadecyl chloride obtained above in 100 ml of tetrahydrofuran was added dropwise over 2 hours while stirring. After the dropwise addition was completed, the resulting white precipitate was filtered, and tetrahydrofuran and triethylamine were removed from the filtrate using a rotary evaporator to obtain a product. It was confirmed by NMR measurement that the obtained compound was a hydrophobic monomer (hydrophobic monomer 3) derived from a necessary structural unit of the copolymer of the present invention represented by the following formula (31).

Hydrophobic monomer 3

<2> Synthesis of the copolymer of the present invention (1) Synthesis of copolymers of Example 1 and Comparative Example 1

In a flask equipped with a nitrogen introduction tube, a cooler and a stirring device, measure 24.0 g of hydrophobic monomer 1 (Production Example 4) and methoxypolyethylene glycol (23) methacrylate (manufactured by Nippon Oil & Fats Co., Ltd.) , Trade name "Blenmer PME-1000") 90.0g, isopropyl alcohol 300ml, phosphate buffer solution (pH 6.8) (made by NACALAI TESQUE (share)) 300ml and stirred to mix. While stirring, nitrogen substitution was performed for 1 hour. A solution in which 2.0 g of ammonium persulfate was dissolved in 20 ml was added thereto, and the reaction was continued for 10 hours at 65° C. (the copolymer of Comparative Example 1 was synthesized under the same conditions for 16 hours). After the reaction, the aqueous solution of sodium hydroxide was used to adjust the pH to 7.0, and the isopropyl alcohol was removed by a rotary evaporator to obtain an aqueous solution of the copolymer of Example 1 (treated under the same conditions to obtain an aqueous solution of the copolymer of Comparative Example 1) .

The weight average molecular weight (in terms of polystyrene) of the copolymer of Example 1 was determined by GPC to be 61,000. In addition, when measured by NMR, the mass ratio of the constituent unit (a) to the constituent unit (b) is about 3:7.

On the other hand, the weight average molecular weight of the copolymer of Comparative Example 1 was 122500, and the mass ratio of the structural unit (a) to the structural unit (b) was about 3:7.

(2) Synthesis of copolymers of Examples 2-8

By the same method as the above (1), a copolymer having a structure shown in Table 2, a weight average molecular weight, and a mass ratio of the structural unit (a) to the structural unit (b) was synthesized. The weight average molecular weight of the copolymer is adjusted by changing the reaction time. In addition, the mass ratio of the constituent unit (a) to the constituent unit (b) can be adjusted by adjusting the molar ratio of the addition amounts of the hydrophobic monomer and the hydrophilic monomer added to the reaction solution.

Furthermore, Examples 2 to 6 are copolymers synthesized using hydrophobic monomer 1. In addition, Example 7 is a copolymer synthesized using the hydrophobic monomer 2 and Example 8 is a copolymer synthesized using the hydrophobic monomer 3.

<Test Example 1>

A 2% by mass aqueous solution of the copolymers of Examples 1 to 6 and Comparative Example 1 was prepared. Each copolymer aqueous solution was applied to the skin of three specialized sensory evaluators, and the elasticity was evaluated according to the following criteria. The results are shown in Table 3.

‧Elasticity

◎...has a very strong sense of elasticity

○...has a strong sense of elasticity

△...with elasticity

×...not very elastic

As shown in Table 3, when the copolymers of Examples 1 to 6 and Comparative Example 1 having the same constitutional unit (a) are compared, the copolymer aqueous solutions of Examples 1 to 6 are compared to the copolymer aqueous solutions of Comparative Example 1. , Has a strong sense of elasticity. In particular, the copolymers of the invention of Examples 1, 5 and 6 have a very strong elasticity.

The above results show that the copolymer containing the structural unit (a) and the structural unit (b) having a weight average molecular weight of 20,000 to 110,000, and particularly preferably 57,000 to 66000, has a good elasticity.

<Test Example 2>

Using the same method as in Test Example 1, the copolymers of Examples 7 and 8 were also evaluated for elasticity. As a result, it can be seen that the copolymers of Examples 7 and 8 also have an elastic feeling.

This result shows that even if the structure of the constituent unit (a) is changed variously, a copolymer having elasticity can be obtained.

<Test Example 3>

To the 2% by mass aqueous solution of the copolymer of Example 1 or the copolymer of Comparative Example 1, 0.5% by mass of Sanxian gum was added to prepare a gel-like cosmetic. This gel-like cosmetic was applied to the skin of three specialized sensory evaluators similar to Test Example 1, and evaluated for non-sticky feeling, elastic feeling, and moist feeling. The evaluation was based on the feeling of use when applying an emulsion (reference cosmetics) containing trimethyl stearic acid trimethylolpropane to the skin, and the evaluation criteria described below were used. The average value of the evaluation values by three evaluators is shown in Table 4 and Figure 1.

‧Evaluation criteria

4 points...Compared with the touch of the benchmark cosmetic raw materials, better

3 points...the same level of touch as the standard cosmetic ingredients

2 points...close to the touch of the basic cosmetic ingredients, but slightly worse

1 point...comparable to the touch of the benchmark cosmetic raw materials, worse

0 points...comparable to the touch of the benchmark cosmetic ingredients, quite poor

As shown in Table 4 and FIG. 1, the gel-like cosmetics of Example 1 are significantly more elastic than the gel-like cosmetics of Comparative Example 1, and they are also excellent in non-sticky feeling and moist feeling.

The results show that the copolymer containing the structural unit (a) and the structural unit (b) having a weight average molecular weight of 20,000 to 110,000, with elasticity as the first priority, is not sticky and moist.

By stirring and mixing the components of Tables 5 to 7 below, an emulsified composition was produced.

Furthermore, in this embodiment, as the water-soluble copolymer of the emulsifier of the present invention, methacrylic acid methacrylate, which is a hydrophobic monomer diglyceryl diisostearate, and a hydrophilic monomer, are used. Ester PEG-23 is a copolymer of (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) with an average molecular weight of 61,000 copolymerized at a mass ratio of about 3:7.

As a water-soluble copolymer, PEG/PPG-60/11 glycerin (ADEKANOL M-3228) of polyoxypropylene (degree of polymerization 60) and polyoxyethylene (average degree of polymerization 11) and ether of glycerin is used The composition (Comparative Examples 2, 4, 6) was produced.

Furthermore, polyoxyethylene hardened castor oil was used as a surfactant to produce an emulsified composition (Comparative Examples 3, 5, and 7).

The three-component system phase diagram plotting the blend ratio of the glyceryl diisostearate methacrylate/methoxymethyl propionate PEG-23 copolymers of Examples 9 to 31 with squalane and water Shown in Figure 2.

Blending ratio of the copolymers of (glyceryl diisostearate methacrylate/methoxymethyl propionate PEG-23) of Examples 32 to 62 with tri(octanoic acid/capric acid) glyceride and water The three-component system phase diagram of the drawing is shown in FIG. 3.

A 3-component system phase diagram plotting the blending ratio of the copolymers of Examples 63-89 (glyceryl diisostearate methacrylate/methoxymethyl methionate PEG-23) with silin and water Shown in Figure 4.

The emulsified compositions of Examples 9 to 89 showed stable emulsified forms even after storage at room temperature for 3 months. That is, with the (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer, even in the use of non-polar hydrocarbon oil squalane, polar hydrocarbon oil three In the case of (octanoic acid/capric acid) glyceride and silicone oil, stable emulsified compositions can also be produced.

On the other hand, the compositions of Comparative Examples 2, 4 and 6 of PEG/PPG-60/11 glycerin containing a water-soluble copolymer cannot be emulsified even after stirring and mixing, and immediately after production, they were completely separated into an oil phase and water box.

This result shows that the water-soluble copolymer of the emulsifier according to the present invention can produce a stable emulsified composition using various oils.

In addition, as shown in Tables 5 to 7, the content of (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer is any formula of 1 to 30% by mass , Can also produce emulsified compositions.

Furthermore, as shown in Tables 5 to 7, even if the content of the oil phase is any of 10 to 70% by mass, an emulsified composition can be produced.

Appropriate amounts of Examples 9 to 89 and Comparative Examples 3, 5, and 7 were applied to the skin. As a result, the emulsified compositions of Examples 9 to 89 had no irritation and were less sticky than the emulsified compositions of Comparative Examples 3, 5, and 7.

This result shows that the emulsified composition emulsified by the water-soluble copolymer of the emulsifier of the present invention has a better usability than the general emulsified composition emulsified by the surfactant.

In particular, the emulsified composition of the embodiment in which the content of the (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer is 15% by mass, more preferably 1% by mass, has More excellent sense of use.

<Production Example 7>

The facial cleansers of Examples 90 to 92 and Comparative Examples 8 and 9 were manufactured according to the recipes shown below. That is, by separately heating the components of α and β to 80° C., adding β to α while stirring and stirring, and cooling, a facial cleanser is obtained.

In addition, as the water-soluble copolymer, glyceryl diisostearate methacrylate, which is a hydrophobic monomer, and methoxymethacrylate PEG-23, which is a hydrophilic monomer, were used in an amount of about 3:7. Copolymer of (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) with an average molecular weight of 61,000.

<Test Example 4>

Let a skilled evaluator use the facial cleansers of Examples 90 to 92 and Comparative Examples 8 and 9 to wash the face. The foamability and foam quality during use and the non-tightness and stickiness of the skin after washing The feeling was evaluated according to the following evaluation criteria. The results are shown in Table 8.

‧Foaming

◎...very good lathering

○...so bubbly

△...weak foaming

×...no blistering

‧Foam quality

◎...very dense foam quality

○...Dense foam quality

△...not too dense

△...not dense

‧No tension

◎...no tension

○...Almost no tightness

△...with a sense of tension

×... has a strong sense of tension

‧No sticky slip

◎...no stickiness

○... almost no sticky slip

△...Slim and slippery

×... has a strong sticky slip

As shown in Table 8, the facial cleanser of Comparative Example 8 has a strong feeling of tightness on the skin after washing the face. On the other hand, the facial cleansers of Examples 90 to 92 have almost no tightness after washing the face.

This result shows that the (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer can reduce the tightness of the skin due to fatty acid soap.

Also, in the facial cleanser of Comparative Example 9 containing carboxymethylcellulose of a water-soluble polymer instead of (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer No good foaming properties of fatty acid soap are seen. On the other hand, the facial cleansers of Examples 90 to 92 showed good foamability.

This result shows that according to the (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer, it does not hinder the good foamability of the fatty acid soap and can reduce the skin after use Sense of tightness.

In addition, as shown in Table 8, the facial cleansing agents of Examples 91 and 92 showed more excellent foaming properties than the facial cleansing agent of Comparative Example 8.

This result shows that by making the content of the (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer 0.8% by mass or more, the foamability of the fatty acid soap can be improved.

In addition, as shown in Table 8, the facial cleanser of Comparative Example 9 has a strong sticky feeling on the skin after washing the face. On the other hand, the facial cleansers of Examples 90 to 92 showed little stickiness after washing the face.

The results show that according to the (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer, it does not produce a sticky feeling, and can reduce the skin after the use of the skin cleanser Feeling tight.

In addition, as shown in Table 8, the facial cleansers of Examples 90 and 91 had better stickiness and slippery properties than the facial cleansers of Example 92.

This result shows that by adjusting the content of the (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer to 3% by mass or less, no sticky-slip feeling is generated and the reduction can be achieved The tightness of the skin after using skin cleanser.

<Production Example 8>

By stirring and mixing the ingredients shown in Table 9, the gel facial cleansers of Examples 93 to 96 and Comparative Examples 10 to 12 were obtained.

<Test Example 5>

As in Test Example 4, the skilled evaluator was asked to use a gel facial cleanser to wash his face and apply the cleansing power to the skin The ease of extension and the non-tight feeling of the skin after washing the face were evaluated according to the following evaluation criteria (the evaluation criteria of the non-tight feeling were the same as in Test Example 4). The results are shown in Table 9.

‧Cleaning power

◎...cleaning power is very strong

○...strong cleaning power

△...weak cleaning power

×...cleaning power is very weak

‧Easy to extend skin

◎...very easy to extend

○...easy to extend

△...not easy to extend

×...very difficult to extend

As shown in Table 9, the gel facial cleansers of Comparative Examples 10 and 11 have a strong feeling of tightness on the skin after washing the face. On the other hand, the facial cleansing creams of Examples 93 to 96 showed little tightness after washing the face sense.

This result shows that the (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer can reduce the skin tightness caused by the nonionic surfactant.

In addition, as shown in Table 9, the gel facial cleansers of Examples 94 and 95 had a better effect of reducing the tightness of the skin after use compared to the gel facial cleansing of Example 93.

This result shows that by making the content of the (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer 0.7% by mass or more, the skin after use can be more effectively reduced Feeling tight.

In addition, as shown in Table 9, the gel facial cleansers of Examples 93 to 96 have better cleaning power than the gel facial cleansers of Comparative Examples 10 to 12.

This result shows that according to the (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer, the cleansing power of a skin cleanser containing a nonionic surfactant can be improved.

Furthermore, the gel facial cleanser of Example 95 has better cleaning power than the gel facial cleanser of Examples 93 and 94.

This result shows that by adjusting the content of the (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer to 2% by mass or more, it is possible to increase the content of nonionic surfactants. The cleansing power of skin cleansers.

In addition, as shown in Table 9, the gel facial cleanser of Example 94 has better spreadability to the skin than the gel facial cleanser of Examples 93 and 95.

This result shows that by adjusting the content of the (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer to 0.6 to 3% by mass, the use of the gel facial cleanser can be improved The ease of extension to the skin.

In addition, the gel facial cleanser of Example 91 and the gel facial cleanser of Example 93 have the same content of nonionic surfactant, but the types are different. However, as shown in Table 9, these two types of gel facial cleansers exhibited the same effects in terms of cleansing power, ease of extension to the skin, and no tightness.

This result shows that the skin cleanser contains (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer. The advantageous effect is not influenced by the type of surfactant contained in the skin cleanser.

The results of Test Examples 4 and 5 show that according to the present invention, the feeling of tightness of the skin after use of the skin cleanser can be reduced.

In addition, according to the present invention, it shows that the good effects of a skin cleanser that does not impair good foamability, dense foam quality, and cleansing power, and does not impair the ease of extension to the skin, or While enhancing the aforementioned effects, it reduces the tightness of the skin after use.

<Production Example 9>

Based on the formulation shown in Table 10, the oil-in-water sunscreen cosmetics of Examples 98 to 103 and Comparative Examples 13 to 15 were produced by the following method.

Mix and dissolve (I) by heating to prepare a mixture of oil phase components, and use a disperser to disperse the hydrophobized titanium oxide particles.

Next, (I) is added to the heated (II) and emulsified with a homogenizer. After emulsification, by adding (III) and (IV) and cooling while stirring and mixing, a sunscreen cosmetic is manufactured.

Furthermore, in this example, as the water-soluble copolymer of component (A), glyceryl diisostearate methacrylate, which is a hydrophobic monomer, and methoxy methacrylate, which is a hydrophilic monomer, are used. PEG-23, a copolymer of (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) with an average molecular weight of 61,000 copolymerized at a molar ratio of about 3:7.

<Test Example 6>

The water-in-oil type sunscreen cosmetics prepared in Examples 97 to 102 and Comparative Examples 13 to 15 were evaluated according to the following criteria for emulsification stability and non-sticky feeling and moisturizing feeling during use. The results are shown in Table 10.

‧Emulsion stability (the state when stored at room temperature for 1 month)

◎...the separation of the oil phase cannot be confirmed at all

○...It is almost impossible to confirm the separation of the oil phase

△...An oil film floats on the surface of the preparation

×... The separation of the oil phase is clearly observed

‧No stickiness

◎...no stickiness at all

○... almost no stickiness

△...Sticky

×... quite sticky

‧Moisturizing

◎...Moisture is very strong

○...Strong moisture

△...wetting feeling

×...wetting is very weak

As shown in Table 10, the oil-in-water sunscreen cosmetics of Examples 97 to 102 containing all the components (A) to (D) have good emulsification stability, no stickiness, and moisturizing feeling.

On the other hand, the sunscreen cosmetic of Comparative Example 13 which does not contain the component (A) has a very strong sticky feeling. In addition, Comparative Example 14 which does not contain the component (B) The sunscreen cosmetics and the sunscreen cosmetics of Comparative Example 15 not containing the component (C) had poor emulsification stability.

These results show that the oil-in-water sunscreen cosmetics containing ingredients (A) to (D) have excellent emulsification stability and non-sticky feeling, and have moisturizing properties.

Furthermore, as shown in Table 10, the sunscreen cosmetic of Example 97 containing sodium stearyl lactate as the component (C) is compared with the sunscreen cosmetic of Example 100 containing sodium glyceryl cocoate as the component (C), Emulsion stability is better.

The result shows that the oil-in-water sunscreen cosmetics containing sodium lactyl lactate as the component (C) have good emulsification stability.

In addition, as shown in Table 10, the sunscreen cosmetic of Example 97 containing polyglycerol pentastearate-10 as the component (B) compared with the polyglycerol tristearate-10 as the component (B ) Of the sunscreen cosmetics of Example 101 has excellent emulsification stability.

The result shows that the oil-in-water sunscreen cosmetics containing polyglycerol pentastearate-10 as the component (B) have good emulsification stability.

In addition, as shown in Table 10, the sunscreen cosmetic of Example 97 containing the ultraviolet scattering agent coated with sodium polyacrylate particulate titanium dioxide as the component (D) is more moisturizing than the sunscreen cosmetic of Example 102 not containing the coated particulate titanium dioxide. Feel better.

This result shows that the UV-scattering agent containing surface treatment with sodium polyacrylate, that is, the oil-in-water sunscreen cosmetics containing water-dispersible UV-scattering agent as component (D), has an excellent moisturizing feeling.

In addition, the sunscreen cosmetics of Example 102, compared with the sunscreen cosmetics of Examples 98 and 99, in which the content of component (B) was 0.3% by mass and 7% by mass, respectively, the emulsion stability and non-sticky feeling Excellent.

This result shows that the content of the component (B) is preferably 0.5% by mass or more from the viewpoint of improving the stability of emulsification, and is preferably 5% by mass or less from the viewpoint of suppressing the stickiness.

In addition, the sunscreen cosmetics of Example 97, compared with the sunscreen cosmetics of Examples 98 and 99 with the contents of component (C) being 0.05% by mass and 1.5% by mass, respectively, had better emulsion stability and no stickiness. Excellent.

This result shows that the content of the component (C) is preferably 0.07% by mass or more from the viewpoint of improvement in emulsification stability, and is preferably 1% by mass or less from the viewpoint of suppression of stickiness.

<Production Example 10>

As shown in Table 11, the content of Sanxian gum and amphiphilic copolymer was fixed, and the contents of various 1,3-butanediols (promoting polyols) and glycerin (inhibiting polyols) were changed to prepare and implement Examples 103 to 123 of the composition of the present invention. The relationship between the content of 1,3-butanediol and glycerin in each of the various examples is based on the relationship between the total amount of tri-xanthan gum and the amphiphilic copolymer, as shown in Figure 5 with a 3-component phase diagram Adjustments.

Furthermore, as the amphiphilic copolymer, glyceryl diisostearate methacrylate, which is a hydrophobic monomer, and methoxymethacrylate PEG-23, which is a hydrophilic monomer, are used at a ratio of about 3:7 (Molar ratio copolymerized with an average molecular weight of 61,000 (glyceryl diisostearate methacrylate/methoxymethacrylate PEG-23) copolymer.

In the following test examples, in order to facilitate the observation of the sea-island structure using a microscope, a fluorescent probe "NBD-COCl" was chemically introduced (glyceryl diisostearate methacrylate/ Methacrylate PEG-23) copolymer to prepare a composition.

<Test Example 7> Observation of the sea island structure of the coating

By applying about 0.5 g of the composition of Examples 103 to 123 on a glass slide in the range of about 1.5 cm×1.5 cm, and leaving it at 40° C. for 3 days to evaporate the water in the composition to form on the glass slide Envelope. The configuration of the coatings of Examples 103 to 123 thus formed was observed with a conjugate laser scanning microscope.

As a result, any of the components forms an island structure. FIG. 6 shows micrographs of the compositions of Examples 105, 106, 108, 111, 113, 114, 115, 119, 120, 122, and 123.

As shown in FIG. 6, in the compositions of Examples 115, 119, and 120, agglomeration of island particles was observed, and many island particles with an average particle diameter of more than 10 μm, or island particles with a long axis to short axis ratio of less than 0.5 were observed.

On the other hand, in the compositions of Examples 106 to 114, no aggregation of island particles was observed, and the number of fine island particles with an average particle diameter of 1 to 5 μm had a particle size distribution of 80% or more.

This result shows that a composition in which the total amount of the components shown in the three-component phase diagram of FIG. 5 in the total amount of the water-soluble polymer and the amphiphilic copolymer is 15% by mass or less is unlikely to cause aggregation of island particles.

In addition, no agglomeration of island particles was observed, and the number of fine island particles with an average particle diameter of 1 to 5 μm was 80% or more. The area ratio of the sea phase to island phase of the coatings of Examples 103 to 114 was 6: 4~7: 3.

<Test Example 8> Sensory evaluation

The composition of Example 103 was used by 48 evaluators. For the coating formed on the skin after being applied to the skin, the moist feeling, elasticity, softness, tenderness, swelling, and stickiness were as described in the seventh As shown in the figure, the evaluation is based on 7 points. In addition, commercially available lotions and lotions were used as comparison objects. The results are shown in Figure 7.

In addition, as cosmetics, general substances mainly containing water and containing polyols, known water-soluble polymers, preservatives and extracts are used. In addition, as an emulsion, an oil-in-water emulsified cosmetic containing mineral oil, walnut oil, etc. as an oil phase component is used.

As shown in FIG. 7, for the film formed by applying the composition of Example 103 to the skin, the items of moisturization, elasticity, softness, tenderness, and swelling were obtained in the same way as the emulsion containing oil. High evaluation above it.

Furthermore, as shown in FIG. 7, the film formed by the composition of Example 103 had a significantly less sticky feeling than the emulsion, and the same level as the lotion.

This result shows that the composition of the present invention can form a film having a tactile sensation like milk containing an oil agent on the skin regardless of whether the aqueous component is the main component. In particular, it is shown that the composition of the present invention can achieve both moisturizing properties and softness that are difficult to achieve in cosmetics mainly composed of water-soluble components.

In addition, this result shows that the composition of the present invention has an aqueous component as the main component, and therefore has few disadvantages such as stickiness felt in cosmetics containing oils.

<Production Example 11>

According to the formulation of Table 12, the compositions of the present invention of Examples 124 and 125 were prepared.

The coatings formed by the compositions of Examples 124 and 125 were observed with a microscope in the same manner as in Test Example 8. As a result, no aggregation of island particles was observed in the same manner as the coatings of Examples 103 to 114, and the number of fine island particles with an average particle diameter of 1 to 5 μm had a particle size distribution of 80% or more.

This result shows that even in the case of using a polyquaternium-61 and (glyceryl methacrylate ethyl ester/stearyl methacrylate) copolymer as an amphiphilic copolymer, a good The membrane of the island structure. That is, even in the case of changing various amphiphilic copolymers having a structural unit derived from a hydrophobic monomer and a structural unit derived from a hydrophilic monomer, by combining a water-soluble polymer and water, A composition capable of forming a coating film having a sea-island structure can be prepared.

[Industry availability]

The copolymer of the present invention that solves the first problem can be applied to cosmetics.

The present invention that solves the second problem can be applied to emulsified cosmetics.

The present invention that solves the third and fourth problems can be applied to a facial cleanser.

The present invention that solves the fifth problem can be applied to sunscreen cosmetics.

The present invention that solves the sixth problem can be applied to oil-free cosmetics.

Claims (9)

A copolymer comprising one or two or more structural units (a) derived from a hydrophobic monomer represented by the following general formula (1) and a hydrophilic monomer represented by the following general formula (2) One or two or more structural units derived from the body (b) are necessary structural units and have a weight average molecular weight of 20,000 to 80,000;

(In general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² and R ³ may be the same or different, and represents a branched carbon number having 6 to 22 that does not contain a ring structure. Acyl group; X represents a group desorbing OH group from triol);

(In the general formula (2), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁵ represents an alkylene group having 2 to 4 carbon atoms which may have a hydroxyl group, and R ⁶ represents a hydrogen atom and a carbon atom having 6 to 6 carbon atoms. (10 aromatic hydrocarbon group, aliphatic hydrocarbon group having 1 to 14 carbon atoms or acetyl group having 1 to 12 carbon atoms; n represents an integer of 6 to 40). The copolymer of claim 1, wherein the mass ratio of the constituent unit (a) to the constituent unit (b) is 25:75~35:65. For the copolymer of claim 1 or 2, wherein the molar ratio of the structural unit (a) to the structural unit (b) is 35:65~46:54. The copolymer according to claim 1 or 2, wherein the hydrophobic monomer is a hydrophobic monomer represented by the following general formula (3);

(In general formula (3), R ⁷ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ⁸ and R ⁹ may be the same or different, and represents a branched carbon number having 10 to 22 carbon atoms that does not contain a ring structure. (Acyl group, or an acyl group having 6 or more carbon atoms that does not contain a ring structure and has 2 or more branches; Y represents a group that desorbs an OH group from a triol). The copolymer according to claim 1 or 2, wherein the hydrophilic monomer is a hydrophilic monomer represented by the following general formula (4); general formula (4)

(In general formula (4), R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ¹¹ represents a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms, an aliphatic hydrocarbon group having 1 to 14 carbon atoms or carbon (Acyl groups with numbers 1 to 12; m represents an integer of 6 to 40). The copolymer of claim 1 or 2, wherein the triol is selected from the group consisting of glycerin, trimethylolpropane, and trimethylolethane. The copolymer according to claim 1 or 2, wherein the hydrophobic monomer is a compound represented by the following general formula (5);

(In the general formula (5), R ¹² and R ¹³ may be the same or different, and represent a branched C 18 acyl group that does not contain a ring structure). The copolymer according to claim 1 or 2, wherein the hydrophilic monomer is a hydrophilic monomer represented by the following general formula (6); general formula (6)

(In the general formula (6), l represents an integer of 6 to 40). An external preparation for skin, which contains the copolymer according to any one of claims 1 to 8.

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